bluuebunny/crossref_metadata_2025_split huggingface dataset:
Engineering MoS2 Basal Planes for Hydrogen Evolution via Synergistic Ruthenium Doping and Nanocarbon Hybridization
Authors: Zhang Xing , Zhou Feng , Zhang Shen , Liang Yongye , Wang Ruihu 
Published: March 2019

AbstractPromoting the intrinsic activity and accessibility of basal plane sites in 2D layered metal dichalcogenides is desirable to optimize their catalytic performance for energy conversion and storage. Herein, a core/shell structured hybrid catalyst, which features few‐layered ruthenium (Ru)‐doped molybdenum disulfide (MoS2) nanosheets closely sheathing around multiwalled carbon nanotube (CNT), for highly efficient hydrogen evolution reaction (HER) is reported. With 5 at% (atomic percent) Ru substituting for Mo in MoS2, Ru‐MoS2/CNT achieves the optimum HER activity, which displays a small overpotential of 50 mV at −10 mA cm−2 and a low Tafel slope of 62 mV dec−1 in 1 m KOH. Theoretical simulations reveal that Ru substituting for Mo in coordination with six S atoms is thermodynamically stable, and the in‐plane S atoms neighboring Ru dopants represent new active centers for facilitating water adsorption, dissociation, and hydrogen adsorption/desorption. This work provides a multiscale structural and electronic engineering strategy for synergistically enhancing the HER activity of transition metal dichalcogenides.
Vertically zeolitic imidazolate framework‐L coated mesh with dagger‐like structure for oil/water separation
Authors: Zhang Xuke , Li Hui , Miao Weizhen , Shen Qin , Wang Jing , Peng Donglai , Liu Jindun , Zhang Yatao 
Published: March 2019

AbstractThe novel functional superwettable materials for high‐efficiency oil/water separation are urgently required due to oil pollution in water body caused by oil tanker accidents, seabed oil production, and oil from refineries and petrochemical plants. Here, the superhydrophobic and superoleophilic zeolitic imidazolate framework‐L (ZIF‐L) mesh with antimicrobial effect was successfully fabricated by in‐situ growth, composed of vertically ZIF‐L with micro‐/nanodagger‐like structure and exhibited the water contact angle of 155.4 ± 1.8° and the oil contact angle of 0° in air. Furthermore, ZIF‐L was verified to have an excellent antimicrobial activity, which endowed ZIF‐L mesh with good antimicrobial performance. ZIF‐L mesh provided a permeation flux with 1.75 × 105 L m−2 hr−1 and 99.7% separation efficiency after 10 cycles operations for water mixtures with isooctane and presented optimal stability. Accordingly, the results demonstrated that ZIF‐L as a new material shows an attractive applied promise for oil/water separation in industry.
Liquid jet impaction on the single‐layer stainless steel wire mesh in a rotating packed bed reactor
Authors: Xu Ying‐Chun , Li Yan‐Bin , Liu Ya‐Zhao , Luo Yong , Chu Guang‐Wen , Zhang Liang‐Liang , Chen Jian‐Feng 
Published: March 2019

AbstractLiquid flow behaviors in the packing zone of a rotating packed bed reactor significantly affect the mass transfer performance. However, the interaction between the rotating packing and liquid is still not clear, due to packing's complex structure. In this work, liquid jet impaction on a rotating single‐layer wire mesh was investigated to clarify the interaction and liquid flow behaviors after the impaction was observed and analyzed by visualization and simulation methods. Visual experiments showed that the interaction could be divided into the shearing action generated by vertical fibers and carrying action generated by horizontal fibers of wire mesh. A dimensionless number β was introduced as a criterion to evaluate the influence of these actions on the liquid dispersion. Simulation results agreed well with the experimental results of liquid dispersion. Dynamic liquid film behaviors on the fiber surface were further simulated and the average film thickness was 21–32 μm.
TUM–WelChem cell model for the prediction of liquid distribution in random packed columns
Authors: Hanusch Florian , Kender Robert , Engel Volker , Rehfeldt Sebastian , Klein Harald 
Published: March 2019

AbstractLiquid maldistribution is one of the main deficiencies in random packed column design. Therefore, the knowledge of liquid distribution and its model‐based prediction is of great interest. This work aims to further develop and validate the TUM–WelChem Cell Model for random packed columns. First, cell dimension calculations and the determination of random packing element orientations are standardized. The original WelChem Cell Model applies a liquid distribution mechanism based on liquid spread factors derived by virtual 3D irrigation experiments. An extension of the model involves the implementation of liquid and gas load related distribution mechanisms, considering dispersion effects caused by liquid loading and the countercurrent gas flow. The wall flow is refined by an increase of packing porosity at the column wall. Liquid distribution profiles provided by the TUM–WelChem Cell Model are validated against experimental data and show good agreement for both uniform and point source initial liquid distribution.
Anisotropic membrane materials for gas separations
Authors: Restrepo‐Flórez Juan‐Manuel , Maldovan Martin 
Published: March 2019

AbstractTo date the design of membranes for gas separations has relied on isotropic materials that control the magnitude of mass flux. However, mass flux is a vector quantity and controlling its direction is essential for complete manipulation of diffusion processes. In this article, we show how anisotropic materials enable control of mass flux direction in membranes and allow for novel mechanisms for gas separation. We present a detailed study of the design parameters that control membrane selectivities and permeances and demonstrate that this new class of membranes can provide a new avenue to obtain significant improvements with respect to isotropic materials. We also discuss how the proposed anisotropic membranes can be constructed using isotropic materials. Mass diffusion principles for gas separations in anisotropic membranes are different from those in isotropic materials and this novel strategy for the design of membranes can open new opportunities in membrane separation processes.
Dental microwear texture analysis ofHomo sapienssapiens: Foragers, farmers, and pastoralists
Authors: Schmidt Christopher W. , Remy Ashley , Van Sessen Rebecca , Willman John , Krueger Kristin , Scott Rachel , Mahoney Patrick , Beach Jeremy , McKinley Jaqueline , D'Anastasio Ruggero , Chiu Laura , Buzon Michele , De Gregory J. Rocco , Sheridan Susan , Eng Jacqueline , Watson James , Klaus Haagen , Da‐Gloria Pedro , Wilson Jeremy , Stone Abigail , Sereno Paul , Droke Jessica , Perash Rose , Stojanowski Christopher , Herrmann Nicholas 
Published: March 2019

AbstractObjectivesThe current study seeks to determine if a sample of foragers, farmers, and pastoralists are distinguishable based on their dental microwear texture signatures.Materials and methodsThe study included a sample of 719 individuals from 51 archeological sites (450 farmers, 192 foragers, 77 pastoralists). All were over age 12 and sexes were pooled. Using a Sensofar® white‐light confocal profiler we collected dental microwear texture analysis (DMTA) data from a single first or second molar from each individual. We leveled and cleaned data clouds following standard procedures and analyzed the data with Sfrax® and Toothfrax® software. The DMTA variables were complexity and anisotropy. Statistics included ANOVA with partial eta squared and Hedges's g. We also performed a follow‐up K‐means cluster analysis.ResultsWe found significant differences between foragers and farmers and pastoralists for complexity and anisotropy, with foragers having greater complexity than either the farmers or the pastoralists. The farmers and pastoralists had greater anisotropy than the foragers. The Old World foragers had significantly higher anisotropy values than New World foragers. Old and New World farmers did not differ. Among the Old World farmers, those dating from the Neolithic through the Late Bronze Age had higher complexity values than those from the Iron Age through the medieval period. The cluster analysis discerned foragers and farmers but also indicated similarity between hard food foragers and hard food farmers.DiscussionOur findings reaffirm that DMTA is capable of distinguishing human diets. We found that foragers and farmers, in particular, differ in their microwear signatures across the globe. There are some exceptions, but nothing that would be unexpected given the range of human diets and food preparation techniques. This study indicates that in general DMTA is an efficacious means of paleodietary reconstruction in humans.
Nickel‐Catalyzed Asymmetric Reductive Arylalkylation of Unactivated Alkenes
Authors: Jin Youxiang , Wang Chuan 
Published: March 2019

AbstractReported is an asymmetric reductive dicarbofunctionalization of unactivated alkenes. Under the catalysis of a Ni/BOX system, various aryl bromides, incorporating a pendant olefinic unit, were successfully reacted with an array of primary alkyl bromides in the presence of Zn as a reductant, furnishing a series of benzene‐fused cyclic compounds bearing a quaternary stereocenter in high enantioselectivities. Notably, this reaction avoids the use of pregenerated organometallics and demonstrates high tolerance of sensitive functionalities. The preliminary mechanistic investigations reveal that this Ni‐catalyzed reaction proceeds as a cascade consisting of migratory insertion and cross‐coupling with a nickel(I)‐mediated intramolecular 5‐exocyclization as the enantiodetermining step.
Enantioselective Synthesis of C−N Axially Chiral N‐Aryloxindoles by Asymmetric Rhodium‐Catalyzed Dual C−H Activation
Authors: Li Honghe , Yan Xiaoqiang , Zhang Jitan , Guo Weicong , Jiang Jijun , Wang Jun 
Published: March 2019

AbstractThe first enantioselective Satoh–Miura‐type reaction is reported. A variety of C−N axially chiral N‐aryloxindoles have been enantioselectively synthesized by an asymmetric rhodium‐catalyzed dual C−H activation reaction of N‐aryloxindoles and alkynes. High yields and enantioselectivities were obtained (up to 99 % yield and up to 99 % ee). To date, it is also the first example of the asymmetric synthesis of C−N axially chiral compounds by such a C−H activation strategy.
Intermolecular, Branch‐Selective, and Redox‐Neutral Cp*IrIII‐Catalyzed Allylic C−H Amidation
Authors: Knecht Tobias , Mondal Shobhan , Ye Jian‐Heng , Das Mowpriya , Glorius Frank 
Published: March 2019

AbstractHerein, we report the redox‐neutral, intermolecular, and highly branch‐selective amidation of allylic C−H bonds enabled by Cp*IrIII catalysis. A variety of readily available carboxylic acids were converted into the corresponding dioxazolones and efficiently coupled with terminal and internal olefins in high yields and selectivities. Mechanistic investigations support the formation of a nucleophilic IrIII–allyl intermediate rather than the direct insertion of an Ir–nitrenoid species into the allylic C−H bond.
A Biocompatible Heterogeneous MOF–Cu Catalyst for In Vivo Drug Synthesis in Targeted Subcellular Organelles
Authors: Wang Faming , Zhang Yan , Liu Zhengwei , Du Zhi , Zhang Lu , Ren Jinsong , Qu Xiaogang 
Published: March 2019

AbstractAs a typical bioorthogonal reaction, the copper‐catalyzed azide–alkyne cycloaddition (CuAAC) has been used for drug design and synthesis. However, for localized drug synthesis, it is important to be able to determine where the CuAAC reaction occurs in living cells. In this study, we constructed a heterogeneous copper catalyst on a metal–organic framework that could preferentially accumulate in the mitochondria of living cells. Our system enabled the localized synthesis of drugs through a site‐specific CuAAC reaction in mitochondria with good biocompatibility. Importantly, the subcellular catalytic process for localized drug synthesis avoided the problems of the delivery and distribution of toxic molecules. In vivo tumor therapy experiments indicated that the localized synthesis of resveratrol‐derived drugs led to greater antitumor efficacy and minimized side effects usually associated with drug delivery and distribution.
Fabrication of rubber gel as oil absorbent by using water as porosity agent for oil removal
Authors: Mustapa M. Hilman , Musbah Diana Liza , Sulaiman Nik Muslihuddin Nik , Lazim Azwan Mat 
Published: March 2019

ABSTRACTOil pollution is a crucial issue that has adversed impact not only on the environment but also human beings. As an alternative to all conventional approaches, a porous rubber gel based on liquid natural rubber (LNR) with excellent hydrophobic and wettability properties has been developed using a simple vulcanization reaction. To determine their sorption capability, LNR gel was employed for absorption of various types of oils such as Petrol A, Petrol B, kerosene, diesel, crude oil, and olive oil. The functionality of LNR gel was characterized by Fourier transform infrared spectroscopy and the morphology of LNR gel was observed using a scanning electron microscope. By combining wettability and hydrophobicity, the LNR gel exhibited high oil sorption capacity and selectivity for oil removal from water. The LNR gel was able to absorb oils, especially the low viscosity types. Besides, it can also be reused up to 20 cycles while maintaining its oil sorption performance. The selective absorbent shows the recovery of petrol in the range of 96–99% by squeezing the oil. Thus, LNR gel has great potential as green material for cleaning up oil contaminants on a large scale. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47749.
Fabrication and characterization of poly(vinylidene fluoride)–polytetrafluoroethylene composite membrane for CO2 absorption in gas–liquid contacting process
Authors: Du Mengfan , Gong Huijuan , Pang Honglei , Shen Qi , Chen Zezhi 
Published: March 2019

ABSTRACTThe wetting resistance of poly(vinylidene fluoride) (PVDF) membrane is a critical factor which determines the carbon dioxide (CO2) absorption performance of the gas–liquid membrane contactors. In this study, the composite PVDF–polytetrafluoroethylene (PTFE) hollow fiber membranes were fabricated through dry‐jet wet phase‐inversion method by dispersing PTFE nanoparticles into PVDF solution and adopting phosphoric acid as nonsolvent additive. Compared with the PVDF membrane, the composite membranes presented higher CO2 absorption flux due to their higher effective surface porosity and surface hydrophobicity. The composite membrane with addition of 5 wt % PTFE in the dope gained the optimum CO2 absorption flux of 9.84 × 10−4 and 2.02 × 10−3 mol m−2 s−1 at an inlet gas (CO2/N2 = 19/81, v/v) flow rate of 100 mL min−1 by using distilled water and aqueous diethanolamine solution, respectively. Moreover, the 5% PTFE membrane showed better long‐term stability than the PVDF membrane regardless of different types of absorbent, indicating that polymer blending demonstrates great potential for gas separation. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47767.
Disease Burden in Osteoarthritis Is Similar to That of Rheumatoid Arthritis at Initial Rheumatology Visit and Significantly Greater Six Months Later
Authors: Chua Jacquelin R. , Jamal Shakeel , Riad Mariam , Castrejon Isabel , Malfait Anne‐Marie , Block Joel A. , Pincus Theodore 
Published: March 2019

ObjectiveTo analyze disease burden in osteoarthritis (OA) according to Multidimensional Health Assessment Questionnaire (MDHAQ)/Routine Assessment of Patient Index Data 3 (RAPID3) scores at the initial visit and the 6‐month follow‐up visit, compared with rheumatoid arthritis (RA) as a benchmark for high disease burden.MethodsAll patients with all diagnoses at the Rush University Medical Center Division of Rheumatology complete a paper MDHAQ at all visits, saved as a PDF in the electronic health record. MDHAQ 0–10 scores for physical function, pain, and patient global assessment (compiled into RAPID3 0–30 scores) and additional scales at the initial and 6‐month follow‐up visits, for new OA and RA patients seen from 2011 to 2017, were compared. OA and RA patients were classified as self‐referred or physician‐referred, and RA patients were classified as disease‐modifying antirheumatic drug (DMARD)–naive or having prior‐DMARD treatment. Patient groups were compared using t‐tests and analysis of variance, adjusted for age, disease duration, body mass index (BMI), education, and ethnicity.ResultsCompared with RA patients, OA patients had higher age, BMI, and disease duration. At initial visit, the mean RAPID3 did not differ significantly in OA versus DMARD‐naive RA patients, whether self‐ or physician‐referred (range 14.8–16.4 [P = 0.38]), or in all OA patients versus DMARD‐naive RA patients versus prior‐DMARD RA patients (15.0, 15.7, and 15.8, respectively [P = 0.49]). After 6 months, RAPID3 was improved to 13.3, 10.3, and 10.8, respectively, which represented substantially greater improvement in RA patients than OA patients (P < 0.001). Similar results were seen for most self‐reported measures and in adjusted analyses.ConclusionMDHAQ/RAPID3 scores are similar in OA and RA patients at the initial visit, but higher in OA patients than in RA patients 6 months later, reflecting superior RA treatments. The same MDHAQ/RAPID3 allows comparisons of disease burdens in different diseases.
Randomized, Double‐Blind, Placebo‐Controlled Trial of Intraarticular Trans‐Capsaicin for Pain Associated With Osteoarthritis of the Knee
Authors: Stevens Randall M. , Ervin John , Nezzer Jennifer , Nieves Yeni , Guedes Kimberly , Burges Robin , Hanson Peter D. , Campbell James N. 
Published: March 2019

ObjectiveTo assess the efficacy and safety of high‐purity synthetic trans‐capsaicin (CNTX‐4975) in patients with chronic moderate‐to‐severe osteoarthritis (OA)–associated knee pain.MethodsIn this phase II multicenter double‐blind study, patients ages 45–80 years who had stable knee OA were randomized in a 2:1:2 ratio to receive a single intraarticular injection of placebo, CNTX‐4975 0.5 mg, or CNTX‐4975 1.0 mg. The primary efficacy end point was area under the curve (AUC) for change from baseline in daily Western Ontario and McMaster Universities Osteoarthritis Index pain with walking score (range 0–10, 0 = none and 10 = extreme) through week 12. Secondary efficacy end points included a similar AUC analysis of outcomes in patients treated with CNTX‐4975 0.5 mg, and evaluations extending to 24 weeks.ResultsEfficacy was evaluated in 172 patients (placebo group, n = 69; CNTX‐4975 0.5 mg group, n = 33; CNTX‐4975 1.0 mg group, n = 70). At week 12, greater decreases in the AUC for the pain score were observed with CNTX‐4975 in the 0.5 mg and 1.0 mg groups versus placebo (0.5 mg group least squares mean difference [LSMD] −0.79, P = 0.0740; 1.0 mg group LSMD −1.6, P < 0.0001). Significant improvements were maintained at week 24 in the 1.0 mg group (LSMD −1.4, P = 0.0002). Treatment‐emergent adverse events were similar in the placebo and CNTX‐4975 1.0 mg groups.ConclusionIn this study, CNTX‐4975 provided dose‐dependent improvement in knee OA–associated pain. CNTX‐4975 1.0 mg produced a significant decrease in OA knee pain through 24 weeks; CNTX‐4975 0.5 mg significantly improved pain at 12 weeks, but the effect was not evident at 24 weeks.
Mini‐Generator Based on Self‐Propelled Vertical Motion of a Functionally Cooperating Device Driven by H2‐Forming Reaction
Authors: Zhang Lina , Zhang Xuan , Xiao Meng , Zhang Han , Zhang Yajun 
Published: March 2019

AbstractMini‐generators based on locomotion of small objects have aroused widespread attention because of their potential application in powering small‐scale electronic devices. Although improvements have been made in the development of mini‐generators, there are still some key challenges such as low power output and energy conversion efficiency, which limit the potential application of mini‐generators. Herein, through integrating a superhydrophobic surface, chemical reaction and solenoid coil/magnet into a system, an innovative mini‐generator is designed, which can convert chemical energy into electrical energy through mechanical form. As a result, the energy conversion efficiency and output power are both three hundred times higher than previously reported results and can be applied to power light‐emitting diodes without amplification. We believe that the proposed mini‐generator provides more chance for the application of self‐supplying power sources for electronic devices.
Zur Fortentwicklung des Microplane‐Modells für die numerische Analyse von Betonstrukturen
Authors: Steinke Christian , Zreid Imadeddin , Graf Wolfgang , Kaliske Michael 
Published: March 2019

AbstractWeltweit ist Stahlbeton der meist angewendete Baustoff im Bauwesen. Grundlage einer qualitativ hochwertigen und effizienten deterministischen Analyse ist die nichtlineare numerische Modellierung. Aus der Vielzahl der aktuellen Entwicklungen ist die Beschreibung der Betoncharakteristiken mit dem Microplane‐Modell ausgewählt. Die wesentlichen Aspekte und Vorteile der Vorgehensweisen werden vorgestellt und an sehr anschaulichen praktischen Beispielen gezeigt. Die Implementierung der Modelle in kommerzielle Programme ist weit vorangeschritten, sodass eine breite Nutzung zukünftig möglich sein wird. Der vorliegende Beitrag wurde am 19. Okt. 2018 im Rahmen des 22. Dresdner Baustatik Seminars präsentiert.
Correcting for measurement error in fractional polynomial models using Bayesian modelling and regression calibration, with an application to alcohol and mortality
Authors: Gray Christen M. , Carroll Raymond J. , Lentjes Marleen A. H. , Keogh Ruth H. 
Published: March 2019

AbstractExposure measurement error can result in a biased estimate of the association between an exposure and outcome. When the exposure–outcome relationship is linear on the appropriate scale (e.g. linear, logistic) and the measurement error is classical, that is the result of random noise, the result is attenuation of the effect. When the relationship is non‐linear, measurement error distorts the true shape of the association. Regression calibration is a commonly used method for correcting for measurement error, in which each individual's unknown true exposure in the outcome regression model is replaced by its expectation conditional on the error‐prone measure and any fully measured covariates. Regression calibration is simple to execute when the exposure is untransformed in the linear predictor of the outcome regression model, but less straightforward when non‐linear transformations of the exposure are used. We describe a method for applying regression calibration in models in which a non‐linear association is modelled by transforming the exposure using a fractional polynomial model. It is shown that taking a Bayesian estimation approach is advantageous. By use of Markov chain Monte Carlo algorithms, one can sample from the distribution of the true exposure for each individual. Transformations of the sampled values can then be performed directly and used to find the expectation of the transformed exposure required for regression calibration. A simulation study shows that the proposed approach performs well. We apply the method to investigate the relationship between usual alcohol intake and subsequent all‐cause mortality using an error model that adjusts for the episodic nature of alcohol consumption.