bluuebunny/crossref_metadata_2025_split huggingface dataset:
Effect of Co‐Solvents on the Crystallization and Phase Distribution of Mixed‐Dimensional Perovskites
Authors: Caiazzo Alessandro , Datta Kunal , Jiang Junke , Gélvez‐Rueda María C. , Li Junyu , Ollearo Riccardo , Vicent‐Luna José Manuel , Tao Shuxia , Grozema Ferdinand C. , Wienk Martijn M. , Janssen René A. J. 
Published: October 2021

AbstractSolution‐processed quasi‐2D perovskites are promising for stable and efficient solar cells because of their superior environmental stability compared to 3D perovskites and tunable optoelectronic properties. Changing the number of inorganic layers (n) sandwiched between the organic spacers allows for tuning of the bandgap. However, narrowing the phase distribution around a specific n‐value is a challenge. In‐situ UV–vis–NIR absorption spectroscopy is used to time‐resolve the crystallization dynamics of quasi‐2D butylammonium‐based (BA) perovskites with <n> = 4, processed from N,N‐dimethylformamide (DMF) in the presence of different co‐solvents. By combining with photoluminescence, transient absorption, and grazing‐incidence wide‐angle X‐ray scattering, the crystallization is correlated to the distribution of phases with different n‐values. Infrared spectroscopy and density functional theory reveal that the phase distribution correlates with perovskite precursor—co‐solvent interaction energies and that stronger interactions shift the phase distribution towards smaller n‐values. Careful tuning of the solvent/co‐solvent ratio provides a more homogeneous phase distribution, with highly oriented perovskite crystals and suppressed formation of n = 1–2 phases, providing a power conversion efficiency for BA2MA3Pb4I13 solar cells that increases from 3.5% when processed from DMF to over 11% and 10% when processed from DMF/dimethyl sulfoxide and DMF/N‐methyl‐2‐pyrrolidone mixtures, respectively.
Lanthanum induced lattice strain improves hydrogen sulfide capacities of copper oxide adsorbents
Authors: Canning Griffin A. , Azzam Sara A. , Hoffman Adam S. , Boubnov Alexey , Alshafei Faisal H. , Ghosh Richa , Ko Brian , Datye Abhaya , Bare Simon R. , Simonetti Dante A. 
Published: October 2021

AbstractThis work probes the effects of La on reactions involving CuO sorbents and H2S in gaseous streams. La‐CuO sorbents with nominal La/Cu atomic ratios of 1:2 achieved higher capacities (27 and 36 g H2S per 100 g sorbent) compared to CuO sorbents (25 g H2S per 100 g sorbent). Comparison of the La‐CuO sorbents using energy dispersive x‐ray spectroscopy and La L3‐edge XAS suggested that increased capacity resulted from more uniform dispersion of La within the CuO phase (3.3 wt.% vs. 1.0 wt.% La). X‐Ray absorption near edge structure analysis suggested more electron‐rich Cu species in La‐CuO samples, while extended X‐ray absorption fine structure modeling showed an increase in single‐scattering path lengths for neighboring and near‐neighbor atoms. These changes suggest that La induces strain in the Cu‐O lattice, thereby increasing H2S capacity by reducing energy barriers associated with surface reactions between oxygen atoms and adsorbed H2S molecules.
Dramatic decline in a titi monkey population after the 2016–2018 sylvatic yellow fever outbreak in Brazil
Authors: Berthet Mélissa , Mesbahi Geoffrey , Duvot Guilhem , Zuberbühler Klaus , Cäsar Cristiane , Bicca‐Marques Júlio Cèsar 
Published: October 2021

AbstractPlatyrrhini are highly vulnerable to the yellow fever (YF) virus. From 2016 to 2018, the Atlantic Forest of southeast Brazil faced its worst sylvatic YF outbreak in about a century, thought to have killed thousands of primates. It is essential to assess the impact of this epidemic on threatened primate assemblages to design effective conservation strategies. In this study, we assessed the impact of the 2016–2018 YF outbreak on a geographically isolated population of Near Threatened black‐fronted titi monkeys (Callicebus nigrifrons) in two Atlantic Forest patches of the Santuário do Caraça, MG, Brazil. Extensive preoutbreak monitoring, conducted between 2008 and 2016, revealed that the home range and group sizes of the population remained stable. In 2016, the population size was estimated at 53–57 individuals in 11–12 groups. We conducted monitoring and playback surveys in 2019 and found that the population had decreased by 68% in one forest patch and completely vanished in the other, resulting in a combined decline of 80%. We discuss this severe loss of a previously stable population and conclude that it was highly likely caused by the YF outbreak. The remaining population is at risk of disappearing completely because of its small size and geographic isolation. A systematic population surveys of C. nigrifrons, along other sensible Platyrrhini species, is needed to re‐evaluate their current conservation status.
Commercial Cu2Cr2O5Decorated with Iron Carbide Nanoparticles as a Multifunctional Catalyst for Magnetically Induced Continuous‐Flow Hydrogenation of Aromatic Ketones
Authors: Kreissl Hannah , Jin Jing , Lin Sheng‐Hsiang , Schüette Dirk , Störtte Sven , Levin Natalia , Chaudret Bruno , Vorholt Andreas J. , Bordet Alexis , Leitner Walter 
Published: October 2021

AbstractCopper chromite is decorated with iron carbide nanoparticles, producing a magnetically activatable multifunctional catalytic system. This system (ICNPs@Cu2Cr2O5) can reduce aromatic ketones to aromatic alcohols when exposed to magnetic induction. Under magnetic excitation, the ICNPs generate locally confined hot spots, selectively activating the Cu2Cr2O5surface while the global temperature remains low (≈80 °C). The catalyst selectively hydrogenates a scope of benzylic and non‐benzylic ketones under mild conditions (3 bar H2, heptane), while ICNPs@Cu2Cr2O5or Cu2Cr2O5are inactive when the same global temperature is adjusted by conventional heating. A flow reactor is presented that allows the use of magnetic induction for continuous‐flow hydrogenation at elevated pressure. The excellent catalytic properties of ICNPs@Cu2Cr2O5for the hydrogenation of biomass‐derived furfuralacetone are conserved for at least 17 h on stream, demonstrating for the first time the application of a magnetically heated catalyst to a continuously operated hydrogenation reaction in the liquid phase.
A Free Aluminylene with Diverse σ‐Donating and Doubly σ/π‐Accepting Ligand Features for Transition Metals**
Authors: Zhang Xin , Liu Liu Leo 
Published: October 2021

AbstractWe report herein the synthesis, characterization, and coordination chemistry of a free N‐aluminylene, namely a carbazolylaluminylene2 b. This species is prepared via a reduction reaction of the corresponding carbazolyl aluminium diiodide. The coordination behavior of2 btowards transition metal centers (W, Cr) is shown to afford a series of novel aluminylene complexes3–6with diverse coordination modes. We demonstrate that the tri‐active ambiphilic Al center in2 bcan behave as: 1. a σ‐donating and doubly π‐accepting ligand; 2. a σ‐donating, σ‐accepting and π‐accepting ligand; and 3. a σ‐donating and doubly σ‐accepting ligand. Additionally, we show ligand exchange at the aluminylene center providing access to the modulation of electronic properties of transition metals without changing the coordinated atoms. Investigations of2 bwith IDippCuCl (IDipp=1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene) show an unprecedented aluminylene‐alumanyl transformation leading to a rare terminal Cu‐alumanyl complex8. The electronic structures of such complexes and the mechanism of the aluminylene‐alumanyl transformation are investigated through density functional theory (DFT) calculations.
Structural Basis for Inhibition of ROS‐Producing Respiratory Complex I by NADH‐OH
Authors: Vranas Marta , Wohlwend Daniel , Qiu Danye , Gerhardt Stefan , Trncik Christian , Pervaiz Mehrosh , Ritter Kevin , Steimle Stefan , Randazzo Antonio , Einsle Oliver , Günther Stefan , Jessen Henning J. , Kotlyar Alexander , Friedrich Thorsten 
Published: October 2021

AbstractNADH:ubiquinone oxidoreductase, respiratory complex I, plays a central role in cellular energy metabolism. As a major source of reactive oxygen species (ROS) it affects ageing and mitochondrial dysfunction. The novel inhibitor NADH‐OH specifically blocks NADH oxidation and ROS production by complex I in nanomolar concentrations. Attempts to elucidate its structure by NMR spectroscopy have failed. Here, by using X‐ray crystallographic analysis, we report the structure of NADH‐OH bound in the active site of a soluble fragment of complex I at 2.0 Å resolution. We have identified key amino acid residues that are specific and essential for binding NADH‐OH. Furthermore, the structure sheds light on the specificity of NADH‐OH towards the unique Rossmann‐fold of complex I and indicates a regulatory role in mitochondrial ROS generation. In addition, NADH‐OH acts as a lead‐structure for the synthesis of a novel class of ROS suppressors.
Palladium/Ferrierite versus Palladium/SSZ‐13 Passive NOx Adsorbers: Adsorbate‐Controlled Location of Atomically Dispersed Palladium(II) in Ferrierite Determines High Activity and Stability**
Authors: Khivantsev Konstantin , Wei Xinyi , Kovarik Libor , Jaegers Nicholas R. , Walter Eric D. , Tran Pascaline , Wang Yong , Szanyi János 
Published: October 2021

AbstractPd‐loaded FER and SSZ‐13 zeolites as low‐temperature passive NOx adsorbers (PNA) are compared under practical conditions. Vehicle cold start exposes the material to CO under a range of concentrations, necessitating a systematic exploration of the effect of CO on the performance of isolated Pd ions in PNA. The NO release temperature of both adsorbers decreases gradually with an increase in CO concentration from a few hundred to a few thousand ppm. This beneficial effect results from local nano‐“hot spot” formation during CO oxidation. Dissimilar to Pd/SSZ‐13, increasing the CO concentration above ≈1000 ppm improves the NOx storage significantly for Pd/FER, which was attributed to the presence of Pd ions in FER sites that are shielded from NOx. CO mobilizes this Pd atom to the NOx accessible position where it becomes active for PNA. This behavior explains the very high resistance of Pd/FER to hydrothermal aging: Pd/FER materials survive hydrothermal aging at 800 °C in 10 % H2O vapor for 16 hours with no deterioration in NOx uptake/release behavior. Thus, by allocating Pd ions to the specific microporous pockets in FER, we have produced (hydro)thermally stable and active PNA materials.
The Mechanism of Piezocatalysis: Energy Band Theory or Screening Charge Effect?
Authors: Wang Kai , Han Chen , Li Jiaquan , Qiu Jieshan , Sunarso Jaka , Liu Shaomin 
Published: October 2021

AbstractPiezocatalysis, a newly emerging catalysis technology that relies on the piezopotential and piezoelectric properties of the catalysts, is attracting unprecedented research enthusiasm for applications in energy conversion, organic synthesis, and environmental remediation. Despite the rapid development in the past three years, the mechanism of piezocatalysis is still under debate. A fundamental understanding of the working principles of this technology should enable the future design and optimization of piezocatalysts. Herein, we provide an overview of the two popular theories used to explain the observed piezocatalysis: energy band theory and screening charge effect. A comprehensive discussion and clarification of the differences, relevance, evidence, and contradiction of the two mechanisms are provided. Finally, challenges and perspectives for future mechanistic studies are highlighted. Hopefully, this Review can help readers gain a better understanding of piezocatalysis and enable its application in their own research.
Electron Localization and Lattice Strain Induced by Surface Lithium Doping Enable Ampere‐Level Electrosynthesis of Formate from CO2
Authors: Yan Shuai , Peng Chen , Yang Chao , Chen Yangshen , Zhang Junbo , Guan Anxiang , Lv Ximeng , Wang Haozhen , Wang Zhiqiang , Sham Tsun‐Kong , Han Qing , Zheng Gengfeng 
Published: October 2021

AbstractThe electrochemical CO2 conversion to formate is a promising approach for reducing CO2 level and obtaining value‐added chemicals, but its partial current density is still insufficient to meet the industrial demands. Herein, we developed a surface‐lithium‐doped tin (s‐SnLi) catalyst by controlled electrochemical lithiation. Density functional theory calculations indicated that the Li dopants introduced electron localization and lattice strains on the Sn surface, thus enhancing both activity and selectivity of the CO2 electroreduction to formate. The s‐SnLi electrocatalyst exhibited one of the best CO2‐to‐formate performances, with a partial current density of −1.0 A cm−2 for producing formate and a corresponding Faradaic efficiency of 92 %. Furthermore, Zn–CO2 batteries equipped with the s‐SnLi catalyst displayed one of the highest power densities of 1.24 mW cm−2 and an outstanding stability of >800 cycles. Our work suggests a promising approach to incorporate electron localization and lattice strain for the catalytic sites to achieve efficient CO2‐to‐formate electrosynthesis toward potential commercialization.
π‐Lewis‐Base‐Catalyzed Asymmetric Vinylogous Umpolung Reactions of Cyclopentadienones and Tropone
Authors: Yang Xing‐Xing , Yan Ru‐Jie , Ran Guang‐Yao , Chen Chen , Yue Jing‐Fei , Yan Xiao , Ouyang Qin , Du Wei , Chen Ying‐Chun 
Published: October 2021

AbstractWe disclose that the carbonates of 4‐hydroxy‐2‐cyclopentenones can form π‐allylpalladium‐based 1,2‐carbodipoles, which isomerize to interesting η2‐Pd0‐cyclopentadienone complexes. Compared with the labile parent cyclopentadienone, the HOMO energy of the related η2‐complex was significantly raised via the back‐bonding of Pd0 as a π‐Lewis base, rendering the uncoordinated C=C bond an electron‐richer dienophile in inverse‐electron‐demand aza‐Diels–Alder‐type reactions with diverse 1‐azadienes. The vinylogous (aza)Morita–Baylis–Hillman or cross Rauhut–Currier addition to (imine)carbonyls or activated alkenes, respectively, was also realized to afford chiral [4+2] or [2+2] cycloadducts, respectively, after trapping the re‐generated π‐allylpalladium species. New C1‐symmetric ligands from simple chiral sources were developed, exhibiting high stereoselectivity even with racemic substrates via an unusual dynamic kinetic resolution process. Besides, tropone could be similarly activated by a Pd0 complex.
Characterization, theoretical investigation, and biological applications of Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) complexes of a triazene ligand containing a benzothiazole ring
Authors: Alamri Mona A. , Al‐Jahdali Mutlaq. , Al‐Radadi Najlaa S. , Hussien Mostafa A. 
Published: October 2021

AbstractHerein, Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) complexes of a previously synthesized triazene ligand, namely, (E)‐2‐(3‐(4‐nitrophenyl)triaz‐1‐en‐1‐yl)benzo[d]thiazole (L), were prepared. The metal:ligand ratio of complexes was determined by molar ratio method, and complexes were synthesized based on the result ratio (1:2 for Co(II), Ni(II), and Zn(II) complexes, and (1:1) for Cu(II) and Mn(II)). The complexes were characterized by infrared (IR) and electron paramagnetic resonance (EPR) spectroscopies, magnetic moment, and/or molar conductance measurements. IR spectra suggested the existence of bidentate binding through the nitrogen atom of the thiazole ring and nitrogen atom of the triazene linkage. Molar conductivities indicated the non‐electrolytic nature of all the complexes. Magnetic moment and EPR of the complexes confirmed their octahedral geometries. Thermal studies were conducted to confirm the structures and analyze the thermal stabilities of the complexes. Activation thermodynamic parameters were determined using the Coats–Redfern and Horowitz–Metzger methods. The calf thymus DNA binding activity was investigated by absorption titration experiments and viscosity measurements, and intrinsic binding constants of complexes range from 4.00 × 105 to 5.00 × 105 M−1. Cytotoxic activities were examined against MCF‐7 and HCT‐116 cell lines. Although all the complexes exhibited reasonable cytotoxic effects, their cytotoxic activities were in the following order: Zn(II) > Cu(II) > Mn(II) > Co(II) > Ni(II). Zn(II) complex showed the highest activity with IC50 values are 2.87 and 1.94 μg ml−1 against MCF‐7 and HCT‐116, respectively. Molecular docking was used to assess the binding affinities of these complexes to colon cancer (3ig7) and breast cancer (1hk7) proteins. Zn(II) complex showed the best docking scores compared with the ligand and other tested complexes. Results of molecular docking well correlated with those of the cytotoxicity experiments.
High‐throughput screening for distinguishing nitrilases from nitrile hydratases in Aspergillus and application of a Box–Behnken design for the optimization of nitrilase
Authors: Santos Edvan do Carmo , de Menezes Luiz Henrique Sales , Santos Carolline Silva , Santana Paulo Vinicius Bispo , Soares Glêydison Amarante , Tavares Iasnaia Maria de Carvalho , Freitas Janaina de Silva , de Souza‐Motta Cristina Maria , Bezerra José Luiz , da Costa Andréa Miura , Uetanabaro Ana Paula Trovatti , Porto André Luiz Meleiro , Franco Marcelo , de Oliveira Julieta Rangel 
Published: October 2021

AbstractNitrilases and nitrile hydratases/amidases hydrolyze nitriles into carboxylic acids and/or amides, which are used in industrial chemical processes. In the present study, 26 microorganisms, including yeasts and filamentous fungi, in a minimum solid mineral medium supplemented with glucose and phenylacetonitrile were screened to evaluate their biocatalytic potential. Of these microorganisms, five fungi of the genus Aspergillus were selected and subjected to colorimetry studies to evaluate the production and distinction of nitrilase and nitrile hydratase/amidase enzymes. Aspergillus parasiticus Speare 7967 and A. niger Tiegh. 8285 produced nitrilases and nitrile hydratase, respectively. Nitrilase optimization was performed using a Box–Behnken design (BBD) and fungus A. parasiticus Speare 7967 with phenylacetonitrile volume (μl), pH, and carbohydrate source (starch:glucose; g/g) as independent variables and nitrilase activity (U ml–1) as dependent variable. Maximum activity (2.97 × 10–3 U ml–1) was obtained at pH 5.5, 80 μl of phenylacetonitrile, and 15 g of glucose. A. parasiticus Speare 7967 showed promise in the biotransformation of nitriles to carboxylic acids.
Pod‐Like Fe7S8@N−C Nanowires for High Performance Sodium Ion Batteries
Authors: Dong Yaqian , Zhang Yaohui , Wang Nana , Zou Guifu , Zhang Qiang , Gan Shengquan , He Liang , Bai Zhongchao 
Published: October 2021

AbstractOne dimensional Fe7S8@N−C nanocomposite, consisting of Fe7S8 nanoparticles homogeneously embedded in N‐doped carbon nanowires, was synthesized by a facile hydrothermal‐annealing process. As an anode material for sodium‐ion batteries, the electrode exhibited capacities of 481 mA h g−1 after 1000 cycles at 5 A g−1 and 591 mA h g−1 at 200 mA g−1 with a retention ratio of 91 %. The excellent rate performance and cycling stability can be attributed to the synergistic effects of the one‐dimensional N‐doped carbon and ultra‐small Fe7S8 particles, which will improve electrical conductivity and alleviate the volume expansion of the electrode during cycling. This work will afford a great reference for further development of iron sulfides‐based anode materials towards high‐performance sodium‐ion batteries.
Celiac artery dissection in polycystic kidney disease
Authors: Yamamoto Koichiro , Hasegawa Kou , Oka Kosuke , Otsuka Fumio 
Published: October 2021

AbstractAutosomal‐dominant polycystic kidney disease (ADPKD) is rarely complicated by celiac artery dissection. Dissection of the aorta and its major branches should be carefully differentiated in ADPKD patients with acute‐onset abdominal pain.
Abrupt Spin‐State Switching in Mn(III) Complexes with BPh4 Anion: Effect of Halide Substituents on Crystal Structure and Magnetic Properties.
Authors: Tiunova Aleksandra V. , Kazakova Anna V. , Korchagin Denis V. , Shilov Gennady V. , Zorina Leokadiya V. , Simonov Sergey V. , Zakharov Konstantin V. , Vasiliev Aleksander N. , Yagubskii Eduard B. 
Published: October 2021

AbstractThree tetraphenylborates of mononuclear Mn(III) cation complexes with hexadentate ligands, the products of the reaction between a N,N′‐bis(3‐aminopropyl)ethylenediamine and salicylaldehydes with the different haloid substitutions at the 5 or 3,5 positions, have been synthesized: [Mn(5‐F‐sal‐N‐1,5,8,12)]BPh4 (1), [Mn(3,5‐diCl‐sal‐N‐1,5,8,12)]BPh4 (2) and [Mn(3,5‐Br,Cl‐sal‐N‐1,5,8,12)]BPh4 (3). Their crystal structure, dielectric constant (ϵ) and magnetic properties have been studied. Ligand substituents have a dramatic effect on the structure and magnetic properties of the complexes. With decreasing temperature, the complex (1) shows a gradual spin crossover from the high‐spin state (HS) to the HS:LS intermediate phase, followed by an abrupt transition to the low‐spin state (LS) without changing the crystal symmetry. The complexes 2 and 3 are isostructural, but have fundamentally different properties. Complex 2 demonstrates two structural phase transitions related to sharp spin crossovers from the HS to the HS:LS intermediate phase at 137 K and from the intermediate phase to the LS at 87 K, while complex 3 exhibits only one spin transition from the HS to the HS:LS intermediate phase at 83 K.
Variable Luminescence and Chromaticity of Homoleptic Frameworks of the Lanthanides together with Pyridylpyrazolates
Authors: Youssef Heba , Sedykh Alexander E. , Becker Jonathan , Schäfer Thomas , Taydakov Ilya V. , Li Huanrong R. , Müller‐Buschbaum Klaus 
Published: October 2021

AbstractHomoleptic, 3D coordination polymers of the formula 33∞[Ln(3‐PyPz)3] and 3∞[Ln(4‐PyPz)3], (3‐PyPz)−=3‐(3‐pyridyl)pyrazolate anion, (4‐PyPz)−=3‐(4‐pyridyl)pyrazolate anion, both C8H6N3−, Ln=Sm, Eu, Gd, Tb, Dy, were obtained as highly luminescent frameworks by reaction of the lanthanide metals (Ln) with the aromatic heterocyclic amine ligands 3‐PyPzH and 4‐PyPzH. The compounds form two isotypic series of 3D coordination polymers and exhibit fair thermal stability up to 360 °C. The luminescence properties of all ten compounds were determined in the solid state, with an antenna effect through ligand–metal energy transfer leading to high efficiency of the luminescence displayed by good quantum yields of up to 74 %. The emission is mainly based on ion‐specific lanthanide‐dependent intra 4 f–4 f transitions for Tb3+: green, Dy3+: yellow, Sm3+: orange‐red, Eu3+: red. For the Gd3+‐containing compounds, the yellow emission of ligand triplet‐based phosphorescence is observed at room temperature and 77 K. Co doping of the Gd‐containing frameworks with Eu3+ and Tb3+ allow further shifting of the chromaticity towards white light emission.