bluuebunny/crossref_metadata_2025 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

Substituting 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

A 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

Nicht‐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

A 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

The 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

The 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

Chemo‐ 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

Excellent 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

Perovskite 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

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 < 0·001) and spent a greater number of their last 90 days of life in hospital (median 19 versus 8 days; P < 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 < 0·001; home: 14·5 versus 23·8 per cent, P < 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

X‐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 conclusion

Benzofuran 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 conclusion

Bacteriohopanepolyols 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

Orally 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.
Evaluation of Therapeutics for Severely Debilitating or Life‐Threatening Diseases or Conditions: Defining Scope to Enable Global Guidance Development
Authors: Liu Maggie , Fields F. Owen , Prescott Judith S. , Bello Akintunde , Bower Nancy , Darakjy Salima , Hartke James , Kadambi Vivek , Lapadula Daniel , Stoch Aubrey , Derzi Mazin
Published: October 2019

A significant regulatory gap exists to facilitate global development of therapeutics for nononcology severely debilitating or life‐threatening diseases or conditions (SDLTs). In a 2017 publication, a streamlined approach to the development of treatments for SDLTs was proposed to facilitate earlier and continued patient access to new, potentially beneficial therapeutics.1 However, a major hindrance to broad adoption of this streamlined approach has been the lack of universally accepted, objective criteria to define SDLTs. This article serves to extend the 2017 publication by further addressing the challenge of defining SDLT scope in order to stimulate broader discussion and facilitate development of regional and ultimately international guidelines on the development of therapeutics for SDLTs. Using case examples, we describe key attributes of SDLTs and provide criteria for consideration of an SDLT scope definition.
Weak Intramolecular Interactions to Stabilize Supramolecular Fullerene‐Porphyrin Conjugates and to Control the Conformation of Multiporphyrinic Arrays
Authors: Nierengarten Jean‐François
Published: October 2019

Porphyrins are key building blocks for the construction of photoactive supramolecular ensembles and molecular machines. As part of this research, our group is involved in a program on the development of supramolecular systems combining porphyrin building blocks with fullerene acceptors, and different strategies have been developed to obtain stable, non‐covalent conjugates. These results are described in the first part of this review with special emphasis on positive cooperative effects resulting from the existence of secondary weak intramolecular interactions in the supramolecular assemblies. On the other hand, our group has also developed multiporphyrinic arrays to generate supramolecular ensembles mimicking the primary events observed in the natural photosynthetic system, in particular light harvesting devices in which multiporphyrinic antenna collect light and channel the absorbed energy to a single energy acceptor. During this work, weak intramolecular coordination interactions have been observed between metalloporphyrins and triazole subunits allowing us to control the conformation of complex multiporphyrinic arrays. Based on this observation, we have designed molecular machines mimicking the blooming of a flower. These results are described in the second part of the present review.
Temperature‐Triggered Switchable Dielectric Constants in Zinc‐Based Hybrid Organic‐Inorganic Compounds: (C3H6NH2)2[ZnX4] (X = Cl and Br)
Authors: Shi Chao , Hua Miao‐Miao , Gong Zhi‐Xin , Ma Jia‐Jun , Wang Chang‐Feng , Liang Hao , E Dian‐Yu , Qi Fang‐Wei , Zhang Yi , Ye Heng‐Yun
Published: October 2019

Two new zinc‐based hybrid organic‐inorganic compounds (AZT)2[ZnX4] (AZT = azetidine cation; X = Cl, 1; Br, 2) were successfully synthesized as high‐temperature stimuli‐responsive materials. Systematic thermodynamic characterization demonstrated that they undergo reversible structural phase transitions accompanied by switchable dielectric constant centered at 342 K for 1 and 356 K for 2, respectively. Variable‐temperature single‐crystal X‐ray analysis and dielectric constant measurements disclosed the order‐disorder transformation of the cation and anion contributed to the desirable electrical properties. As expected, the static‐motional transition in crystal structure arouses dielectric transitions between the low‐ and high‐dielectric states, making them a type of switchable dielectric materials.
Metal‐Catalyzed Hydrofunctionalization Reactions of Haloalkynes
Authors: Cadierno Victorio
Published: October 2019

Metal‐catalyzed hydrofunctionalization reactions of alkynes, i.e. the addition of E–H units (E = heteroatom or carbon) across the C≡C bond, are of key importance in modern synthetic chemistry. In recent years, haloalkynes have been successfully involved in these types of transformations, thus opening new atom‐economical routes for the generation, among others, of haloalkenes, a pivotal class of compounds for cross‐coupling processes. In particular, several catalytic systems able to promote the selective addition of C–H, O–H, N–H, S–H and X–H (X = halide) bonds to haloalkynes have been reported. This chemistry is comprehensively discussed in this Minireview article.
Mizoroki–Heck Cross‐Coupling of Acrylate Derivatives with Aryl Halides Catalyzed by Palladate Pre‐Catalysts
Authors: Islam Mohammad Shahidul , Nahra Fady , Tzouras Nikolaos V. , Barakat Assem , Cazin Catherine S. J , Nolan Steven P. , Al‐Majid Abdullah Mohammed
Published: October 2019

The Mizoroki–Heck (MH) reaction involving aryl halides with various acrylates and acrylamides has been studied using air and moisture‐stable imidazolium‐based palladate pre‐catalysts. These pre‐catalysts can be converted into Pd‐NHC species (NHC = N‐heterocyclic carbene) under catalytic conditions and are capable of facilitating the Mizoroki–Heck reaction of aryl halides with various acrylates. The effects of solvent, catalyst loading, temperature and bases on the reaction outcome have been investigated. Various coupling partners were tolerated under the optimal reaction conditions catalyzed by palladate 1, [SIPr·H][Pd(η3‐2‐Me‐allyl)Cl2]. The efficiency of the optimized synthetic methodology was tested on various aryl halides and substituted acrylates as well as acrylamides. The MH reaction yielded the coupled products in good to excellent isolated yields (up to 98%).
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

The 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.
Yes‐Associated Protein in Kupffer Cells Enhances the Production of Proinflammatory Cytokines and Promotes the Development of Nonalcoholic Steatohepatitis
Authors: Song Kyoungsub , Kwon Hyunjoo , Han Chang , Chen Weina , Zhang Jinqiang , Ma Wenbo , Dash Srikanta , Gandhi Chandrashekhar R. , Wu Tong
Published: October 2019

Background and Aims

Yes‐associated protein (YAP) plays an important role in hepatocarcinogenesis, although the potential role of YAP in non‐neoplastic liver diseases remains largely unknown. We report herein that YAP in Kupffer cells (KCs) enhances the production of proinflammatory cytokines and promotes the development of nonalcoholic steatohepatitis (NASH). Our data show that the expression of YAP is significantly increased in KCs of wild‐type mice fed a high‐fat diet (HFD).

Approach and Results

We generated mice with macrophage/monocyte‐specific deletion of YAP (YAPϕKO) or Toll‐like receptor 4 (TLR4; TLR4ϕKO), and animals were fed an HFD or treated with lipopolysaccharide (LPS). Our data showed that YAPϕKO mice fed an HFD exhibited lower serum alanine aminotransferase (ALT)/aspartate aminotransferase (AST) levels and less hepatic inflammation when compared to their littermate controls. LPS treatment induced accumulation of YAP in KCs in vitro and in mice, which was prevented by macrophage/monocyte‐specific deletion of TLR4 (TLR4ϕKO). LPS transcriptionally activates YAP through activator protein 1 in macrophages/KCs. LPS‐induced YAP further enhances expression of proinflammatory cytokines (including monocyte chemoattractant protein 1, tumor necrosis factor alpha, and interleukin 6) through YAP association with the TEA domain–binding motif in the promoter region of inflammatory cytokines. Forced overexpression of active YAP (YAP5SA) in KCs enhanced the production of proinflammatory cytokines. Treatment of HFD‐fed mice with verteporfin inhibited KC activation, reduced liver inflammation, and decreased serum ALT/AST levels. Analyses of liver tissues from NASH patients reveal that YAP is increased in KCs and that level of YAP in human liver tissues is positively correlated with expression of proinflammatory cytokines.

Conclusions

This study describes an important role of YAP in KCs for regulation of liver inflammation in NASH. Our findings suggest that inhibition of YAP may represent an effective therapeutic strategy for NASH treatment.
Inhibition of BAG‐1 induced SH‐SY5Y cell apoptosis without affecting Hsp70 expression
Authors: Song Yan‐Kun , Li Zhi , Wang Yun , Qu Yan , Li Qing‐Shu , Man Xiao‐Yun , Wang Feng‐Tao , Hu Dan
Published: October 2019

Objective

To further explore the role of BCL‐2 associated anthanogen‐1 (BAG‐1) in neuronal apoptosis and whether the effect of BAG‐1 depends on heat shock protein 70 (HSP70).

Methods

RNA interference (RNAi) technology was used to inhibit the expression of BAG‐1 in SH‐SY5Y cells. Hypoxia‐reoxygenation injury model in the SH‐SY5Y cells was established. Cell Counting Kit‐8 (CCK‐8) was performed for cell viability. Annexin V‐APC/7‐AAD double‐staining followed by flow cytometry was used to measure cell apoptosis. Quantitative reverse‐transcription polymerase chain reaction and Western blot analysis were used to detect the messenger RNA (mRNA) and protein expression of genes, respectively.

Results

BAG‐1 gene silencing decreased SH‐SY5Y cell viability and promoted SH‐SY5Y cell apoptosis after hypoxia‐reoxygenation. However, the down‐regulation of BAG‐1 had no effect on the mRNA and protein expression of HSP70.

Conclusion

BAG‐1 could protect SH‐SY5Y cells from the hypoxia‐reoxygenation injury without affecting HSP70 expression.
Exploring African‐American womens' experiences with substance use treatment: A review of the literature
Authors: Redmond Michelle L. , Smith Sharla , Collins Tracie C.
Published: October 2019

The aim of this systematic review is to synthesize evidence on treatment barriers among African‐American women who seek treatment for substance use disorders. The authors reviewed articles from 1995 to 2018 on the topic of substance use disorders among African‐American women. Based on the review of 13 articles, we found African‐American women were more likely to encounter treatment readiness barriers compared to access barriers and system‐related barriers. Personal and interpersonal barriers were more readily identified throughout the literature reviewed. However, African‐American women did encounter other barriers such as access‐ and system‐related barriers. In addition, the intersection of race, gender, and class was not addressed in the specific articles, but should be considered when working to remove treatment barriers for this population. While prevalence of alcohol and drug use is limited among African‐American women, it is important to understand how treatment readiness barriers may limit successful completion of treatment and ongoing progress. Implications for treatment and future research in addressing barriers to treatment for African‐American women are discussed.
What is the profile of workers who build effective relationships with young people facing severe and multiple disadvantages?
Authors: Sandu Rebeca D.
Published: October 2019

Family‐like professional helping relationships have the potential to alter the trajectories of young people facing significant disadvantage. This study seeks to identify the worker attributes that allow the formation of deep bonds with young people in these circumstances. Access to young people in difficult circumstances was secured via organisations that provided support to this population. Interviews about positive‐helping relationships were conducted with young people (n = 30) and support workers (n = 35) from 11 UK and 5 US not‐for‐profit organisations. Thematic analysis was used to analyse the data. Three sets of worker qualities were identified and linked to how relationships change young people's trajectories in the context of adversity. This study has implications for the selection, training, and support of workers who provide support to young people facing difficult challenges underscoring the qualities needed to provide support and change young people's outcomes.
Short communication comments on ‘DISO: A rethink of Taylor diagram’
Authors: Xu Zhongfeng , Han Ying
Published: October 2019

In a recent article, Hu et al. (2019) argued that the commonly used Taylor diagram in climate model evaluation only considered centred statistics, while the absolute error (AE) was not considered. Therefore, they proposed a new index, termed Distance between Indices of Simulation and Observation (DISO), that takes AE, correlation coefficient, and uncentred RMSE into account to comprehensively measure climate model performance. Note that the widely used uncentred RMSE is a function of the AE and correlation coefficient. Therefore, it is not necessary to combine AE and correlation coefficient with the uncentred RMSE again to define DISO. In addition, model performance does not improve monotonically with the decrease in the DISO index, which is also a flaw of the index. Indeed, the Taylor diagram was constructed based on the cosine law between three‐centred statistics that cannot measure the mean error of the climate model. However, this limitation can be mitigated by showing the mean error or percent bias on the diagram or constructing the Taylor diagram with uncentred statistics. The uncentred statistics still satisfy the cosine law and can also be illustrated in the Taylor diagram. In our viewpoint, there is nothing wrong with the Taylor diagram. On the contrary, the Taylor diagram can effectively visualize multiple statistics and compare the performance of different climate models.
Collagen Coating Effects on Fe–Mn Bioresorbable Alloys
Authors: Huang Sabrina , Ulloa Ana , Nauman Eric , Stanciu Lia
Published: October 2019

Bioresorbable iron‐manganese alloys (Fe‐30%Mn) are considered as one of the next‐generation resorbable materials for orthopedic applications. Previous in vitro study showed that Fe30Mn scaffolds with 10% porosity displayed strong mechanical properties and adequate degradation rate without severe cytotoxicity effect. However, the cellular compatibility of these alloys in terms of cell‐to‐cell and alloy‐to‐cell interactions is not ideal. Collagen is the most abundant protein in human bone, providing structural support beneficial to bone healing. We hypothesized that coating collagen on Fe30Mn can improve osteointegration or activities promoting cell adhesion, migration, and proliferation, as the alloy degrades. After preparing collagen coating on Fe‐30Mn via spin coating, we conducted a corrosion test and a direct cytotoxicity test on four Fe30Mn groups: non‐porous and 10% porosity, with and without collagen coating. Furthermore, we evaluated and compared the morphologies of cells over a period of 7 days. Results showed that there was no significant difference between the collagen‐coated and non‐coated groups in corrosion rates, yet a significant decrease from the porous non‐coated group to the porous collagen‐coated group in cytotoxicity level was found. Cell morphology on the porous non‐coated group displayed round shape, whereas that on the porous collagen‐coated group displayed flattened spreading. The study showed that the collagen coating significantly increased the initial cell viability and adhesion for both the porous and non‐porous groups without impeding their degradation rates. © 2019 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 38:523–535, 2020
Staphylococcus aureus Prosthetic Joint Infection Is Prevented by a Fluorine‐ and Phosphorus‐Doped Nanostructured Ti–6Al–4V Alloy Loaded With Gentamicin and Vancomycin
Authors: Auñón Álvaro , Esteban Jaime , Doadrio Antonio L. , Boiza‐Sánchez Macarena , Mediero Aranzazu , Eguibar‐Blázquez Diego , Cordero‐Ampuero José , Conde Ana , Arenas María‐Ángeles , de‐Damborenea Juan‐José , Aguilera‐Correa John J.
Published: October 2019

Prosthetic joint infection (PJI) is one of the most devastating complications in orthopedic surgery. One approach used to prevent PJI is local antibiotic therapy. This study evaluates the antibiotic release, in vitro cytocompatibility and in vivo effectiveness in preventing PJI caused by Staphylococcus aureus (S. aureus) of the fluorine‐ and phosphorus‐doped, bottle‐shaped, nanostructured (bNT) Ti–6Al–4V alloy loaded with a mixture of gentamicin and vancomycin (GV). We evaluated bNT Ti–6Al–4V loading with a mixture of GV, measuring the release of these antibiotics using high‐performance liquid chromatography. Further, we describe bNT Ti–6Al–4V GV cytocompatibility and its efficacy against S. aureus using an in vivo rabbit model. GV was released from bNT Ti–6Al–4V following a Boltzmann non‐linear model and maximum release values were obtained at 240 min for both antibiotics. The cell proliferation of MCT3T3‐E1 osteoblastic cells significantly increased at 48 (28%) and 168 h (68%), as did the matrix mineralization (52%) of these cells and the gene expression of three of the most important markers related to bone differentiation (more than threefold for VEGF and BGLAP, and 65% for RunX) on bNT Ti–6Al–4V GV compared with control. In vivo study results show that bNT Ti–6Al–4V GV can prevent S. aureus PJI according to histopathological and microbiological results. According to our results, bNT Ti–6Al–4V loaded with a mixture of GV using the soaking method is a promising biomaterial with favorable cytocompatibility and osteointegration, demonstrating local bactericidal properties against S. aureus. © 2019 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 38:588–597, 2020
Degrees of categoricity of trees and the isomorphism problem
Authors: Mahmoud Mohammad Assem
Published: October 2019

In this paper, we show that for any computable ordinal α, there exists a computable tree of rank with strong degree of categoricity if α is finite, and with strong degree of categoricity if α is infinite. In fact, these are the greatest possible degrees of categoricity for such trees. For a computable limit ordinal α, we show that there is a computable tree of rank α with strong degree of categoricity (which equals ). It follows from our proofs that, for every computable ordinal , the isomorphism problem for trees of rank α is ‐complete.
High Thermal Conductivity Nanocomposites Based on Conductive Polyaniline Nanowire Arrays on Boron Nitride
Authors: Bai Yufeng , Han Weifang , Ge Chunhua , Liu Rui , Zhang Rui , Wang Lixia , Zhang Xiangdong
Published: October 2019

With the development of soft electronics, conductive composites are garnering an increasing amount of attention. The electrical conductivity, thermal conductivity, and electrical stability of conductive composites are all very important. In particular, the thermal conductivity of conductive composites is critical to the stability of their conductive properties. However, little is reported on thermal management in conductive systems. Herein, sufficiently hydroxylated boron nitride nanosheets (BN‐OH)@polyaniline (PANI) composite nanosheets with a high thermal conductivity and outstanding conductance stability are reported. PANI nanowire arrays are aligned vertically on BN‐OH. This well‐ordered nanostructure provides the means to form a good conductive and thermally conductive path. Notably, the composite through‐plane thermal conductivity is 2.1 W m−1 K−1(≈1000% that of pure PANI) and that the resistivity of the composite is 1.38 Ω cm. Importantly, the resistivity of the composite remains unchanged after 1 h of work. The results show that this composite has prospective applications for use in soft electronics.
M‐constants in Orlicz–Lorentz function spaces
Authors: Cui Yunan , Foralewski Paweł , Hudzik Henryk
Published: October 2019

In this paper some lower and upper estimates of M‐constants for Orlicz–Lorentz function spaces for both, the Luxemburg and the Amemiya norms, are given. Since degenerated Orlicz functions φ and degenerated weighted sequences ω are also admitted, this investigations concern the most possible wide class of Orlicz–Lorentz function spaces. M‐constants were defined in 1969 by E. A. Lifshits, and used by many authors in the study of lattice structures on Banach spaces, as well as in the fixed point theory.
UK seniors' antidepressant use doubled in last two decades
Authors: Canady Valerie A.
Published: October 2019

Noting that depression is a leading cause of disability with older people particularly susceptible to poor outcomes, researchers have found that the proportion of people over 65 on antidepressants in the UK has more than doubled in 20 years. The new research, “Changing Prevalence and Treatment of Depression Among Older People Over Two Decades,” is published in the British Journal of Psychiatry.
Automated polyp segmentation for colonoscopy images: A method based on convolutional neural networks and ensemble learning
Authors: Guo Xudong , Zhang Na , Guo Jiefang , Zhang Huihe , Hao Youguo , Hang Jingqing
Published: October 2019

Purpose

To automatically and efficiently segment the lesion area of the colonoscopy polyp image, a polyp segmentation method has been presented.

Methods

An ensemble model of pretrained convolutional neural networks was proposed, using Unet‐VGG, SegNet‐VGG, and PSPNet. Firstly, the Unet‐VGG is obtained by the first 10 layers of VGG16 as the contraction path of the left half of the Unet. Then, the SegNet‐VGG is acquired by fine‐tuned transfer learning VGG16, using the first 13 layers of VGG16 as the encoder of the SegNet and combined the original decoder of the SegNet. By adjusting the input size of the Unet‐VGG, SegNet‐VGG, and PSPNet, the preprocessed data can be correctly fed to the three network models. The three models are used as the basic trainer to train and segment the datasets. Based on the ensemble learning algorithm, the weight voting method is used to ensemble the segmentation results corresponding to single basic trainer.

Results

Both IoU and DICE similarity score were used to evaluate the segmentation quality for cvc300 with 300 images, CVC‐ClinicDB with 612 images, and ETIS‐LaribPolypDB with 196 images. From the experimental results, the IoU and DICE obtained by the proposed method for the cvc300 datasets can reach up to 96.16% and 98.04%, respectively, the IoU and DICE for the CVC‐ClinicDB datasets can reach up to 96.66% and 98.30%, respectively, whereas the IoU and DICE for the ETIS‐LaribPolypDB datasets can reach up to 96.95% and 98.45%, respectively. Evaluation of the IoU and DICE in our methods shows higher accuracy than previous methods.

Conclusions

The experimental results show that the proposed method improved correspondingly in IoU and DICE compared to a single basic trainer. The range of improvement is 1.98%–6.38%. The proposed ensemble learning succeeds in automatic polyp segmentation, which potentially helps to establish more polyp datasets.
Metal‐Based Electrocatalysts for Methanol Electro‐Oxidation: Progress, Opportunities, and Challenges
Authors: Tong Yueyu , Yan Xiao , Liang Ji , Dou Shi Xue
Published: October 2019

Direct methanol fuel cells (DMFCs) are among the most promising portable power supplies because of their unique advantages, including high energy density/mobility of liquid fuels, low working temperature, and low emission of pollutants. Various metal‐based anode catalysts have been extensively studied and utilized for the essential methanol oxidation reaction (MOR) due to their superior electrocatalytic performance. At present, especially with the rapid advance of nanotechnology, enormous efforts have been exerted to further enhance the catalytic performance and minimize the use of precious metals. Constructing multicomponent metal‐based nanocatalysts with precisely designed structures can achieve this goal by providing highly tunable compositional and structural characteristics, which is promising for the modification and optimization of their related electrochemical properties. The recent advances of metal‐based electrocatalytic materials with rationally designed nanostructures and chemistries for MOR in DMFCs are highlighted and summarized herein. The effects of the well‐defined nanoarchitectures on the improved electrochemical properties of the catalysts are illustrated. Finally, conclusive perspectives are provided on the opportunities and challenges for further refining the nanostructure of metal‐based catalysts and improving electrocatalytic performance, as well as the commercial viability.
Epitaxial Growth of Topological Insulators on Semiconductors (Bi2Se3/Te@Se) toward High‐Performance Photodetectors
Authors: Zhang Ye , Zhang Feng , Xu Yiguo , Huang Weichun , Wu Leiming , Dong Zhijun , Zhang Yupeng , Dong Biqing , Zhang Xiuwen , Zhang Han
Published: October 2019

Heterojunctions, composed of different materials, are widely explored in optoelectronic devices thanks to their unique advantages, such as high carrier mobility and excellent photoelectronic characteristics. In this work, Bi2Se3/Te@Se heterojunctions (Bi2Se3/Te@Se) are synthesized through the epitaxial growth of Bi2Se3 nanosheets (Bi2Se3 NTs) on tellurium@selenium nanotubes (Te@Se NTs) by using a low‐cost and facile solvothermal process. Bi2Se3/Te@Se are further applied in high‐performance photoelectrochemical (PEC)‐type photodetection due to the advantages of broadband optical response and fast carrier relaxation time. The PEC results demonstrate that the as‐prepared photodetectors have pronounced photoresponse behavior from the ultraviolet to visible band with self‐driven ability and excellent long‐term stability. It is anticipated that this work provides a new strategy for epitaxial growth of topological insulators on semiconductors for designing new heterojunctions toward high‐performance optoelectronic devices.