bluuebunny/crossref_metadata_2025_split huggingface dataset:
Li[Ni0.9Co0.09W0.01]O2: A New Type of Layered Oxide Cathode with High Cycling Stability
Authors: Ryu Hoon‐Hee , Park Kang‐Joon , Yoon Dae Ro , Aishova Assylzat , Yoon Chong S. , Sun Yang‐Kook 
Published: October 2019

AbstractSubstituting W for Al in the Ni‐rich cathode Li[Ni0.885Co0.10Al0.015]O2 (NCA89) produces Li[Ni0.9Co0.09W0.01]O2 (NCW90) with markedly reduced primary particle size. Particle size refinement considerably improves the cathode's cycling stability such that the NCW90 cathode retains 92% of its initial capacity after 1000 cycles (compared to 63% for NCA89), while the cathode produces a high initial discharge capacity of 231.2 mAh g−1 (at 0.1 C). Thus, the proposed NCW90 can deliver high energy density and a long battery lifetime simultaneously, unlike other Ni‐rich layered oxide cathodes. This unprecedented cycling stability is mainly attributed to a series of interparticular microfractures that absorb the anisotropic lattice strain caused by a deleterious phase transition near the charge end, thereby improving the cathode's resistance to fracture. Microcrack suppression preserves the mechanical integrity of the cathode particles during cycling and protects the particle interior from detrimental electrolyte attack. The proposed NCW90 cathode provides an improved material from which a new series of Ni‐rich layered cathode can be developed for next‐generation electric vehicles.
A multiple mechanism model for measuring extra‐ and intraparticle mass transport in ion exchange resins
Authors: Nesbitt Allan , Petersen Jochen 
Published: October 2019

AbstractA diffusion‐based kinetic model for resin‐based ion exchange is proposed that simultaneously describes extra‐ and intraparticle diffusion for the purpose of predicting batch transient adsorption rates during resin operation. The extraparticle diffusion is simulated through Newton's‐law‐of‐cooling assuming a stagnant laminar layer, while the intraparticle simulation assumes a homogeneous internal pore environment and uses the Nernst–Planck equation to describe multi‐ion diffusion. The key parameters of the model are the mass transfer coefficient, the intrinsic diffusivities of the adsorbing and desorbing ions and the equilibrium coefficient associated with the Mass‐Action‐Law, which is assumed to be applicable at the liquid/resin interface. A novel method is described to determine the critically important ion concentration at the interface from experiment. Kinetic tests are undertaken in a closed circuit system, adsorbing Na, Mg, and Ba ions separately onto gel type acid resin, and the simulation is fitted to the measured raw data using the Hook–Jeeves search algorithm. The intraparticle diffusivities of the three ions are hence measured and reported.
Evolvierte aliphatische Halogenasen ermöglichen die regiokomplementäre C‐H‐Funktionalisierung einer hochwertigen Chemikalie
Authors: Hayashi Takahiro , Ligibel Mathieu , Sager Emine , Voss Moritz , Hunziker Jürg , Schroer Kirsten , Snajdrova Radka , Buller Rebecca 
Published: October 2019

AbstractNicht‐Häm‐Eisen(II)‐Halogenasen sind wertvolle Biokatalysatoren für die stereo‐ und enantioselektive Halogenierung von nicht‐aktivierten sp3‐Kohlenstoffatomen. Das Substratspektrum dieser Enzyme ist jedoch eng auf natürliche Substrate beschränkt. Hier haben wir die Halogenase WelO5* zur Chlorierung eines pharmazeutisch interessanten Martinellin‐Fragments verändert. Durch Evolution konnten wir eine Halogenase entwickeln, die eine mehr als 290‐fach höhere katalytische Produktivität und 400‐fach höhere scheinbare Wechselzahl (app. kcat) als der Wildtyp aufweist. Wir konnten Schlüsselpositionen im aktiven Zentrum identifizieren, die die Derivatisierung unterschiedlicher Positionen im Substrat erlauben. Wir liefern das erste Beispiel für das Engineering von Nicht‐Häm‐Eisen(II)‐Halogenasen zur Erweiterung des Substratspektrums über die nativen Indolalkaloide hinaus. Die Evolvierbarkeit von WelO5* unterstreicht den Nutzen dieser Enzymfamilie für die Halogenierung von komplexen Chemikalien.
Highly Regio‐, Diastereo‐, and Enantioselective Synthesis of Tetrahydroazepines and Benzo[b]oxepines through Palladium‐Catalyzed [4+3] Cycloaddition Reactions
Authors: Trost Barry M. , Zuo Zhijun 
Published: October 2019

AbstractA novel Pd0‐catalyzed asymmetric [4+3] annulation reaction of two readily accessible starting materials has been developed for building seven‐membered heterocyclic architectures. The potential [3+2] side pathway could be suppressed though fine tuning of the conditions. A broad scope of cycloaddition donors and acceptors participated in the transformation with excellent chemo‐, regio‐, diastereo‐, and enantioselectivtities, leading to valuable tetrahydroazepines and benzo[b]oxepines.
Magnetic Field Directed Rare‐Earth Separations
Authors: Higgins Robert F. , Cheisson Thibault , Cole Bren E. , Manor Brian C. , Carroll Patrick J. , Schelter Eric J. 
Published: October 2019

AbstractThe separation of rare‐earth ions from one another is challenging due to their chemical and physical similarities. Nearly all rare‐earth separations rely upon small changes in ionic radii to direct speciation or reactivity. Herein, we show that the intrinsic magnetic properties of the rare‐earth ions impact the separations of light/heavy and selected heavy/heavy binary mixtures. Using TriNOx3− ([{(2‐tBuNO)C6H4CH2}3N]3−) rare‐earth complexes, we efficiently and selectively crystallized heavy rare earths (Tb–Yb) from a mixture with light rare earths (La and Nd) in the presence of an external Fe14Nd2B magnet, concomitant with the introduction of a concentration gradient (decrease in temperature). The optimal separation was observed for an equimolar mixture of La:Dy, which gave an enrichment factor of EFLa:Dy=297±31 for the solid fraction, compared to EFLa:Dy=159±22 in the absence of the field, and achieving a 99.7 % pure Dy sample in one step. These results indicate that the application of a magnetic field can improve performance in a molecular separation system for paramagnetic rare‐earth cations.
Base‐Stabilized [PO]+/[PO2]+ Cations
Authors: Zhou Jiliang , Liu Liu Leo , Cao Levy L. , Stephan Douglas W. 
Published: October 2019

AbstractThe salts [(BAC)2PO][BF4] (5) and [(BAC)2PO2][BF4] (4) (BAC=bis(diisopropylamino) cyclopropenylidene), consisting of the PO+ and PO2+ cations, respectively, coordinated to the singlet carbenes, have been prepared. Computational investigations reveal that the electronic structure of the PO+ cation is a hybrid between the charge‐localized and charge‐delocalized resonance forms, resulting in ambiphilic reactivity. Compound 5 reacts as a donor with the transition‐metal complex K2PtCl4 to furnish [[(BAC)2PO]2PtCl2][BF4]2 (6) and KCl. Remarkably, both 5 and 4 have shown to act as electrophiles undergoing reactions with fluoride anion, leading to [OPF2]− and (BAC)PO2F, respectively.
Regioselective Hydrosilylation of Olefins Catalyzed by a Molecular Calcium Hydride Cation
Authors: Schuhknecht Danny , Spaniol Thomas P. , Maron Laurent , Okuda Jun 
Published: October 2019

AbstractChemo‐ and regioselectivity are often difficult to control during olefin hydrosilylation catalyzed by d‐ and f‐block metal complexes. The cationic hydride of calcium [CaH]+stabilized by an NNNN macrocycle was found to catalyze the regioselective hydrosilylation of aliphatic olefins to give anti‐Markovnikov products, while aryl‐substituted olefins were hydrosilyated with Markovnikov regioselectivity. Ethylene was efficiently hydrosilylated by primary and secondary hydrosilanes to give di‐ and monoethylated silanes. Aliphatic hydrosilanes were preferred over other commonly employed hydrosilanes: Arylsilanes such as PhSiH3underwent scrambling reactions promoted by the nucleophilic hydride, while alkoxy‐ and siloxy‐substituted hydrosilanes gave isolable alkoxy and siloxy calcium derivatives.
Role of the Iodide–Methylammonium Interaction in the Ferroelectricity of CH3NH3PbI3
Authors: Breternitz J. , Lehmann F. , Barnett S. A. , Nowell H. , Schorr S. 
Published: October 2019

AbstractExcellent conversion efficiencies of over 20 % and facile cell production have placed hybrid perovskites at the forefront of novel solar cell materials, with CH3NH3PbI3 being an archetypal compound. The question why CH3NH3PbI3 has such extraordinary characteristics, particularly a very efficient power conversion from absorbed light to electrical power, is hotly debated, with ferroelectricity being a promising candidate. This does, however, require the crystal structure to be non‐centrosymmetric and we herein present crystallographic evidence as to how the symmetry breaking occurs on a crystallographic and, therefore, long‐range level. Although the molecular cation CH3NH3+ is intrinsically polar, it is heavily disordered and this cannot be the sole reason for the ferroelectricity. We show that it, nonetheless, plays an important role, as it distorts the neighboring iodide positions from their centrosymmetric positions.
Enhanced Lifetime and Photostability with Low‐Temperature Mesoporous ZnTiO3/Compact SnO2Electrodes in Perovskite Solar Cells
Authors: Guo Fengwan , Sun Xiangyu , Liu Bing , Yang Zijiang , Wei Jing , Xu Dongsheng 
Published: October 2019

AbstractPerovskite solar cells (PSCs) with power conversion efficiencies (PCEs) of 25 % mainly have SnO2or TiO2as electron‐transporting layers (ETLs). Now, zinc titanate (ZnTiO3, ZTO) is proposed as mesoporous ETLs owing to its weak photo‐effect, excellent carrier extraction, and transfer properties. Uniform mesoporous films were obtained by spinning coating the ZTO ink and annealed below 150 °C. Photovoltaic devices based on Cs0.05FA0.81MA0.14PbI2.55Br0.45perovskite sandwiched between SnO2‐mesorporous ZTO electrode and Spiro‐OMeTAD layer achieved the PCE of 20.5 %. The PSCs retained more than 95 % of their original efficiency after 100 days lifetime test without being encapsulated. Additionally, the PSCs retained over 95 % of the initial performance when subjected at the maximum power point voltage for 120 h under AM 1.5 G illumination (100 mW cm−2), demonstrating superior working stability. The application of ZTO provides a better choice for ETLs of PSCs.
End-of-life care following leg amputation in patients with peripheral artery disease or diabetes
Authors: de Mestral C , Hsu A T , Talarico R , Lee D S , Hussain M A , Salata K , Al-Omran M , Tanuseputro P 
Published: October 2019

Abstract

Background
The aim was to characterize end-of-life care in patients who have had a leg amputated for peripheral artery disease (PAD) or diabetes.

Methods
This was a population-based retrospective cohort study of patients with PAD or diabetes who died in Ontario, Canada, between 2011 and 2017. Those who had a leg amputation within 3 years of death were compared with a control cohort of deceased patients with PAD or diabetes, but without leg amputation. The patients were identified from linked health records within the single-payer healthcare system. Place and cause of death, as well as health services and costs within 90 days of death, were compared between the amputee and control cohorts. Among amputees, multivariable regression models were used to characterize the association between receipt of home palliative care and in-hospital death, as well as time spent in hospital at the end of life.

Results
Compared with 213 300 controls, 3113 amputees were less likely to die at home (15·5 versus 24·9 per cent; P &lt; 0·001) and spent a greater number of their last 90 days of life in hospital (median 19 versus 8 days; P &lt; 0·001). Amputees also had higher end-of-life healthcare costs across all sectors. However, receipt of palliative care was less frequent among amputees than controls (inpatient: 13·4 versus 16·8 per cent, P &lt; 0·001; home: 14·5 versus 23·8 per cent, P &lt; 0·001). Among amputees, receipt of home palliative care was associated with a lower likelihood of in-hospital death (odds ratio 0·49, 95 per cent c.i. 0·40 to 0·60) and fewer days in hospital (rate ratio 0·84, 0·76 to 0·93).

Conclusion
Palliative care is underused after amputation in patients with PAD or diabetes, and could contribute to reducing in-hospital death and time spent in hospital at the end of life.
X‐ray Diffraction Mapping for Cultural Heritage Science: a Review of Experimental Configurations and Applications
Authors: Gonzalez Victor , Cotte Marine , Vanmeert Frederik , de Nolf Wout , Janssens Koen 
Published: October 2019

AbstractX‐ray diffraction (XRD) mapping consists in the acquisition of XRD patterns at each pixel (or voxel) of an area (or volume). The spatial resolution ranges from the micrometer (μXRD) to the millimeter (MA‐XRD) scale, making the technique relevant for tiny samples up to large objects. Although XRD is primarily used for the identification of different materials in (complex) mixtures, additional information regarding the crystallite size, their orientation, and their in‐depth distribution can also be obtained. Through mapping, these different types of information can be located on the studied sample/object. Cultural heritage objects are usually highly heterogeneous, and contain both original and later (degradation, conservation) materials. Their structural characterization is required both to determine ancient manufacturing processes and to evaluate their conservation state. Together with other mapping techniques, XRD mapping is increasingly used for these purposes. Here, the authors review applications as well as the various configurations for XRD mapping (synchrotron/laboratory X‐ray source, poly‐/monochromatic beam, micro/macro beam, 2D/3D, transmission/reflection mode). On‐going hardware and software developments will further establish the technique as a key tool in heritage science.
Design, Synthesis and Antifungal Activity of Benzofuran and Its Analogues
Authors: Xu Hang , Hou Zhuang , Liang Zhen , Guo Meng‐Bi , Su Xin , Guo Chun 
Published: October 2019

Summary of main observation and conclusionBenzofuran has antifungal activity as the inhibitor of N‐myristoyltransferase. Twenty‐nine novel benzofuran‐semicarbazide hybrids were designed and synthesized by principle of drug combinationatory. On this basis, the benzofuran ring was simplified to a resorcinol structure, and sixteen novel 1,3‐dialkoxybenzene‐semicarbazide hybrids were designed and synthesized. All structures of the target compounds were characterized by HRMS and NMR. The in vitro antifungal activity of target compounds was evaluated using the microdilution broth method against eight strains of pathogenic fungi with fluconazole as positive control. According to the results of the target compounds, structure‐activity relationship (SAR) is summarized. The inhibitory activity against the tested strains of simplified compounds (K01—K16) has different levels improvement compared with compounds Z01—Z29. K01—K16 showed significant antifungal activities against A. fumigatus, C. kruseii, and sensitive C. albicans 5314. Notably, compounds Z20, Z22, K10, K11 and K16 also displayed different activities against two fluconazole‐resistance strains that were isolated from AIDS patients. The minimal inhibitory concentration (MIC) values against fluconazole‐resistant strains were in the range of 2—8 μg/mL and 4—32μg/mL, respectively. Furthermore, molecular docking was performed to investigate the binding affinities and interaction modes between the target compound and N‐myristoyltransferase.
Radical SAM‐Dependent Adenosylation Involved in Bacteriohopanepolyol Biosynthesis†
Authors: Zhong Yuting , Ji Xinjian , Zhang Qi 
Published: October 2019

Summary of main observation and conclusionBacteriohopanepolyols are a group of triterpenoids that play important roles in regulating bacterial cell membrane function. As an intermediate in bacteriohopanepolyol biosynthesis, adenosylhopane production is related to a putative Fe‐S protein HpnH, but the exact role of this enzyme remains unsolved. Here we report characterization of HpnH as a novel radical S‐adenosylmethionine (SAM) superfamily enzyme. In contrast to almost all the members in the superfamily, HpnH does not initiate the reaction by a hydrogen atom abstraction process. Instead, it catalyzes the adenosylation of hopene via a radical addition reaction to produce adenosylhopane, representing the second example of radical SAM‐dependent adenosylation involved in natural product biosynthesis.
A Pharmacokinetic Bioequivalence Study Comparing Sublingual Riluzole (BHV‐0223) and Oral Tablet Formulation of Riluzole in Healthy Volunteers
Authors: Qureshi Irfan , Lovegren Meghan , Wirtz Victoria , Larouche Richard , Tanguay Mario , Anderson Matt S. , Hartmann Sonja , Coric Vlad , Berman Robert M. 
Published: October 2019

AbstractOrally administered riluzole extends survival in patients with amyotrophic lateral sclerosis, although it has significant shortcomings (eg, adverse events, dysphagic patients) that limit its utility. BHV‐0223 is a Zydis‐based orally disintegrating formulation of riluzole designed for sublingual administration that addresses the limitations of conventional tablets. This study assessed the bioequivalence between 40‐mg BHV‐0223 and standard 50‐mg oral riluzole tablets, and the food effect on BHV‐0223 pharmacokinetics in healthy volunteers. Overall, 133 healthy subjects received BHV‐0223 and riluzole tablets under fasted conditions. Geometric mean ratios for the area under the plasma concentration–time curve (AUC) from time zero to time of last nonzero concentration (AUC0‐t) (89.9%; confidence interval [CI], 87.3%–92.5%), AUC from time zero to infinity (AUC0‐∞) (89.8%; CI, 87.3%–92.4%), and maximum observed concentration (112.7%; CI, 105.5%–120.4%) all met bioequivalence criteria (80%–125%). Subsequently, 67 subjects received BHV‐0223 under fed conditions. The geometric mean ratios of AUC0‐t(91.2%; CI, 88.1–94.3%), and AUC0‐∞(92.0%; CI, 89.0–95.1%) were similar, but maximum observed concentration ratios were not within bioequivalence criteria. BHV‐0223 was well tolerated. This study demonstrated that 40‐mg sublingual BHV‐0223 is bioequivalent to 50‐mg oral riluzole tablets.
Study on the pore evolution law of anthracite coal under liquid nitrogen freeze‐thaw cycles based on infrared thermal imaging and nuclear magnetic resonance
Authors: Chu Yapei , Zhang Dongming 
Published: October 2019

AbstractThe waterless fracturing method with liquid nitrogen (LN2) as the fracturing fluid has been proposed and successfully applied in coalbed methane (CBM) production in recent years. The temperature of the coal reservoir sharply decreases, causing damage to the pore structure of the coal reservoir due to the ultralow temperature of LN2 during fracturing. Thus, in this paper, infrared thermal imaging (ITI) and nuclear magnetic resonance (NMR) were used to measure the temperature distribution and pore evolution law of anthracite coal. The results demonstrate that the temperature of the coal sample after being frozen by LN2 was far less than 0°C, which causes the internal water of the coal sample to freeze and turn into ice and produce a frost‐heave force. In addition, the temperature of the coal samples was not fixed but fluctuated, which led to the formation of a temperature gradient and induced thermal stress. The T2 spectra variation showed that LN2 freeze‐thaw cycles can promote the development of pores in coal samples and enhance the connectivity of pores. Some of the micropores gradually connect and expand to form a large number of mesopores and macropores under the influence of frost‐heave force and thermal stress. The total porosity, residual porosity, and effective porosity increase with the number of LN2 freeze‐thaw cycles. The NMR imaging directly reflects the change characteristics of the internal pore structure before and after LN2 freeze‐thaw, which provide a new way to reveal the pore evolution law of anthracite. These results show that LN2 freeze‐thaw cycles can damage the pore structure of anthracite coal, and a large number of mesopores and macropores are formed to provide channels for CBM migration, which improves the efficiency of LN2 fracturing.
Cure With Interferon‐Free Direct‐Acting Antiviral Is Associated With Increased Survival in Patients With Hepatitis C Virus‐Related Hepatocellular Carcinoma From Both East and West
Authors: Dang Hansen , Yeo Yee Hui , Yasuda Satoshi , Huang Chung‐Feng , Iio Etsuko , Landis Charles , Jun Dae Won , Enomoto Masaru , Ogawa Eiichi , Tsai Pei‐Chien , Le An , Liu Matthew , Maeda Mayumi , Nguyen Brian , Ramrakhiani Nathan , Henry Linda , Cheung Ramsey , Tamori Akihiro , Kumada Takashi , Tanaka Yasuhito , Yu Ming‐Lung , Toyoda Hidenori , Nguyen Mindie H. 
Published: October 2019

Background and Aims
Survival data among patients with hepatitis C virus (HCV)‐related hepatocellular carcinoma (HCC) after achieving sustained virologic response (SVR) with interferon‐free direct‐acting antivirals (DAAs) in both Asian and western countries are limited. Survival rates were compared between patients with HCV‐related HCC who were untreated for HCV and those who achieved SVR.

Approach and Results
Using data from two U.S. and six Asian centers from 2005 to 2017, we categorized 1,676 patients who were mono‐infected with HCV‐related HCC into patients untreated for HCV (untreated group) and DAA‐treated patients with SVR (SVR group) and matched by propensity score matching (PSM); multivariable Cox regression with HCV treatment status as a time‐varying covariate was used to determine mortality risk and landmark analysis to avoid immortal time bias. There were 1,239 untreated patients and 437 patients with SVR. After PSM, background risks of the 321 pairs of matched patients were balanced (all P > 0.05). After time‐varying adjustment for HCV treatment initiation compared with untreated patients, patients with SVR had significantly higher 5‐year overall survival (87.78% vs. 66.05%, P < 0.001). Multivariable Cox regression showed that SVR was independently associated with a 63% lower risk of 5‐year all‐cause mortality (hazard ratio [HR], 0.37; 95% confidence interval [CI], 0.16‐0.83; P = 0.016) and 66% lower risk of 5‐year liver‐related mortality (HR, 0.34; 95% CI, 0.13‐0.88; P = 0.026) with similar trends after removing patients with liver transplants. Landmark analysis at 90, 180, and 360 days showed consistent results (HRs ranged 0.22 to 0.44, all P < 0.05).

Conclusion
In this multinational consortium, patients with HCV‐related HCC who obtained SVR achieved a 60%‐70% improvement in 5‐year survival (both all‐cause and liver related) compared with patients untreated for HCV. Patients eligible for HCC therapy should also be considered for DAA therapy.