bluuebunny/crossref_metadata_2025 huggingface dataset:
Chronic exposure to Pb2+ perturbs ChREBP transactivation and coerces hepatic dyslipidemia
Authors: Vineeth Daniel P. , Kamthan Mohan , Gera Ruchi , Dogra Surbhi , Gautam Krishna , Ghosh Debabrata , Mondal Prosenjit
Published: July 2019

Dysregulated hepatic de novo lipogenesis contributes to the pathogenesis of nonalcoholic fatty liver disease in both humans and rodents. Clinical evidence suggests fatty liver to have a positive correlation with serum lead (Pb2+) levels. However, an exact mechanism of Pb2+‐induced fatty liver progression is still unknown. Here, we show that exposure to Pb2+ regulates ChREBP‐dependent hepatic lipogenesis. Presence of Pb2+ ions within the hepatocytes reduces transcript and protein levels of sorcin, a cytosolic adaptor partner of ChREBP. Adenovirus‐mediated overexpression of sorcin in Pb2+ exposed hepatocytes and an in vivo mouse model ameliorates liver steatosis and hepatotoxicity. Hereby, we present Pb2+ exposure to be a lethal disruptor of lipid metabolism in hepatocytes and highlight sorcin as a novel therapeutic target against Pb2+‐induced hepatic dyslipidemia.
Effect of Filter Functional Coating on Detrimental Nonmetallic Inclusions in 42CrMo4 Steel and Its Resulting Mechanical Properties
Authors: Seleznev Mikhail , Henschel Sebastian , Storti Enrico , Aneziris Christos G. , Krüger Lutz , Weidner Anja , Biermann Horst
Published: July 2019

Carbon‐bonded ceramic foam filters with different functional coatings are immersed in a 42CrMo4 steel melt within a steel casting simulator. The solidified steel is analyzed with respect to the size distribution and the chemical composition of the remaining nonmetallic inclusions (NMI). Cyclic loading and quasi‐static tests are performed to determine the fatigue limit, the strength, deformability, and toughness of the steel after filter immersion. The immersion of filter with calcium hexaluminate (CA6) coating significantly reduces the population of small (4–20 μm) NMIs. This leads to an increased deformability and, thus, ability for energy dissipation during deformation. However, the maximum size of NMIs is increased from 100 to 150 μm, which results in fatigue limit reduction, despite the decrease in NMIs total density. The majority of inclusions are found to be pure alumina. Large (up to 150 μm) plate‐like alumina inclusions introduce most of the detrimental effects on cyclic strength, whereas significant effect on quasi‐static strength is not found.
Decarboxylative Coupling Reaction of 2‐(1H‐Indol‐3‐yl)acetic Acids with Indole, Azaindole, Benzimidazole and Indazole Derivatives
Authors: Pillaiyar Thanigaimalai , Uzair Muhammad , Ullah Saif , Schnakenburg Gregor , Müller Christa E.
Published: July 2019

3,3′‐Diindolylmethanes (DIMs) are an important class of indole alkaloids that exhibit anti‐inflammatory and anti‐cancer effects. Herein, we report on a new, mild and efficient copper(II)‐promoted decarboxylative coupling reaction of 2‐(1H‐indol‐3‐yl)acetic acid derivatives (1 a–h) with a variety of (substituted) indoles (2 a–t) yielding (un)symmetrically substituted DIMs (3 a–z, 3 aa–ai). Reaction of 2‐(1H‐indol‐3‐yl)acetic acid (1 a) with 7‐azaindole led to the 3,3′‐connected DIM analog 5 d, while 4‐, 5‐, and 6‐azaindoles and benzimidazole reacted at the N1‐nitrogen atom. Reaction of 1 a with 1H‐indazoles led to a mixture of 1‐ and 2‐substituted indazole derivatives. The new method allows large‐scale synthesis of biologically active DIMs.

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Enantioselective Synthesis of β‐Methyl Amines via Iridium‐Catalyzed Asymmetric Hydrogenation of N‐Sulfonyl Allyl Amines
Authors: Cabré Albert , Verdaguer Xavier , Riera Antoni
Published: July 2019

The iridium‐catalyzed asymmetric hydrogenation of several N‐sulfonyl allyl amines is reported. All substrates can be easily obtained by the Ir‐catalyzed isomerization of N‐tosylaziridines reported previously. The commercially available threonine‐derived phosphinite (UbaPHOX) iridium complex has been found to be the best catalyst for this catalytic application, affording β‐methyl amines with good to excellent ee values (up to 94%). The synthetic potential of this novel methodology was demonstrated by the formal synthesis of Lorcaserin and LY‐404187.

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Chemoselective Kumada‐Type Iron Catalysis with Alkyl Grignard Reagents: Reductive Cyclization and Cyclomethylation
Authors: Kim Jae Gon , Baek Jong Hwa , Kim Ye Ji , Jang Yu Jeong , Kang Eun Joo
Published: July 2019

A chemoselective reductive cyclization and cyclomethylation reaction of 7‐iodohept‐2‐yne and 7‐iodohepta‐1,2‐diene derivatives has been carried out using an iron catalyst and various alkyl Grignard reagents, resulting in the formation of pyrrolidines, tetrahydrofurans, and carbocycles with an alkene functional group. The reaction is initiated by single‐electron transfer from reduced Fe species to alkyl iodides and the resulting Fe−H or Fe−Me compound differentiated the structures of the cyclized products, which exhibited diverse complexities and synthetic utilities.
Chiral Conflict as a Method to Create Stimuli‐Responsive Materials Based on Dynamic Helical Polymers
Authors: Alzubi Mohammad , Arias Sandra , Rodríguez Rafael , Quiñoá Emilio , Riguera Ricardo , Freire Félix
Published: July 2019

A new multi‐sensor material based on helical copolymers showing the chiral conflict effect have been prepared. It can successfully detect and identify diverse metal cations in solution. The design of this material has taken into account not only the opposite helical senses induced by the two chiral monomers in the copolymer, but also their dynamic behavior. The induced helical sense can thus be enhanced, diminished, or inverted by interaction with different stimuli (that is, metal ions). Thus, depending on both the copolymer compositions (such as monomer ratios and absolute configurations) and the nature of the metal ion, the response of these dynamic helical copolymers to adopt a single‐handed P or M helix is unique, making it possible not only to detect their presence, but also to identify them individually. New multi‐sensors materials based and inspired on this effect should arise in the future choosing appropriate monomers and stimuli.
Hydrated‐Metal‐Halide‐Based Deep‐Eutectic‐Solvent‐Mediated NiFe Layered Double Hydroxide: An Excellent Electrocatalyst for Urea Electrolysis and Water Splitting
Authors: Zhang Chenyun , Chen Tingting , Zhang Hong , Li Zhonghao , Hao Jingcheng
Published: July 2019

The liquid structures of deep eutectic solvents (DESs) based on hydrated metal halides and their application as electrolytes have been widely studied. However, little attention has been paid to the direct use of this type of DES in the preparation of micro‐/nanomaterials. Herein, an FeCl3⋅6 H2O/urea DES was used in the one‐step synthesis of NiFe‐LDH_D with a nanoflower morphology. In alkaline media, this catalyst promoted excellent electrocatalytic activity for the oxidation of urea at potential of 1.32 V (vs. RHE) and for the oxygen‐evolution reaction at a potential of 1.39 V to achieve a current density of 10 mA cm−2. These results were superior to the results with NiFe‐LDH/NF that was obtained from an aqueous solution of FeCl3, as well as most of the previously reported transition‐metal catalysts. Furthermore, NiFe‐LDH_D/NF could be readily implemented as both a cathode and an anode for the electrolysis of urea and water splitting. The use of hydrated‐metal‐halide‐based DESs for the preparation of LDH catalysts through a dipping‐redox strategy should both enrich the research of DESs and offer guidance for the rational surface engineering of catalysts for the electrolysis of urea and overall water splitting with high performance.
Control for networked control systems with packet dropout and delay
Authors: Liang Xiao , Yang Lei , Lu Xiao , Wang Haixia , Zhang Zhiguo
Published: July 2019

This paper mainly focuses on the optimal control and stabilization for networked control systems with packet dropout, measurement delay and input delay. The main contributions are two‐fold. Firstly, a necessary and sufficient condition for the finite horizon optimal control problem is obtained. Secondly, a necessary and sufficient condition for the stabilization problem is developed. Moreover, it has been proved that under standard assumptions the stabilizing condition depends merely on the eigenvalue of the system matrix and the probability of packet dropout which is irrelevant to measurement delay and input delay.
Dynamics and control of singular boolean networks
Authors: Qi Hongsheng , Qiao Yupeng
Published: July 2019

Consider a class of singular Boolean networks, which consist of two parts: difference part and algebraic part. Using the truth matrix of the algebraic part, the trajectories of the networks are obtained and certain properties are investigated. Then the results are extended to Boolean control networks and the controllability of singular Boolean control systems is investigated. Necessary and sufficient conditions are obtained.
Pre‐Clinical Testing of Microwave Radiometer and a Pilot Study on the Screening Inflammation of Knee Joints
Authors: Ravi Vidyalakshmi M. , Sharma Amit K. , Arunachalam Kavitha
Published: July 2019

This article presents the pre‐clinical evaluation of our custom‐built, single‐band microwave radiometer centered at 1.3 GHz for deep tissue thermometry, and a pilot study on volunteers for passive detection of inflammation in knee joints. The electromagnetic (EM) compatibility of the battery‐operated radiometer for clinical use was assessed as per International Special Committee on Radio Interference (CISPR) 22 standard. The ability to detect inflammation in knee joints was assessed using a substrate integrated waveguide antenna connected to the radiometer. EM compatibility tests carried out in the laboratory indicated device immunity to intentional radiated interference up to −20 dBm injected power in the global system for mobile communication frequency band, and pre‐compliance to CISPR 22 standard. Radiometer temperature measurements recorded at the lateral and medial aspects of both knees of 41 volunteers indicated mean temperature greater than 33°C for the diseased sites compared with the mean temperature of 28°C measured for the healthy sites. One‐way analysis of variance statistics indicated significantly (P < 0.005) higher radiometer temperature at the diseased sites unlike the healthy sites. Thus, the EM pre‐compliance of the device and the potential to measure deep tissue inflammation were demonstrated. Bioelectromagnetics. 2019;40:402–411. © 2019 Bioelectromagnetics Society.
Synthesis and Biological Evaluation of Decursinol Derivatives as FoxO‐1 Inhibitors in HepG2 Cells
Authors: Joo Jeong‐Ho , Jung Sun Hwa , Yu Kook Hyun , Cheon Hyae Gyeong
Published: July 2019

Diabetes mellitus type 2 is caused by insulin resistance, often associated with increased hepatic gluconeogenesis. Forkhead box O‐1 (FoxO‐1) is known as a major transcription factor regulating hepatic gluconeogenesis, and the increased FoxO‐1 expression and activity are mainly observed in type 2 diabetic patients. To discover new FoxO‐1 inhibitors, the compounds were newly synthesized from decursinol, which is a molecule isolated from the Angelica gigas and proved to be safe. The compounds were evaluated for in vitro FoxO‐1 inhibitory activity using FoxO‐1 reporter assay in HepG2 cells. Among these, the compounds 2b and 2c exhibited FoxO‐1 inhibitory activity with IC50 values of 98.9 and 123.7 μM, respectively. Moreover, the blood glucose level reduction efficacy of synthesized compound 2b was found similar to that of glimepiride, a commercially available antidiabetic drug and used as a reference (21.6 vs. 21.4%), in alloxan‐induced type 2 diabetes rats. These findings suggest that, the compound 2b has moderate inhibitory activity on FoxO‐1 and possibly resulting in the amelioration of diabetic hyperglycemia.
Maternal use of antibiotics and cancer incidence risk in offspring: A population‐based cohort study in Manitoba, Canada
Authors: Ye Xibiao , Monchka Barret A. , Righolt Christiaan H. , Mahmud Salaheddin M.
Published: July 2019

Several epidemiological studies have found an association between maternal antibiotics use during pregnancy and increased risk of certain cancer types, although conclusions differ between studies. We examined this association in a cohort study including 262 116 mother‐child pairs of Manitoba births between 1996 and 2013. Maternal antibiotics use during prepregnancy (6 months prior to pregnancy) and pregnancy periods was assessed. Children's cancer incidence was tracked up to the end of the follow‐up period (December 2015). We calculated incidence rate and used Cox regression to estimate adjusted hazard ratios (HRs). Antibiotics use during pregnancy was not associated with overall cancer (HR = 1.1, 95% confidence interval 0.9‐1.4), leukemias (1.3, 0.9‐1.8), or acute lymphocytic leukemia (1.1, 0.7‐1.6). The association between antibiotics use and overall cancer risk differed by trimester: 1.5 (1.1‐1.9) in the first, 0.8 (0.6‐1.0) in the second, and 1.1 (0.8‐1.5) in the third trimester. Further research is necessary to confirm the association between first‐trimester exposure and cancer risk after a better controlling of confounding factors.
Homozygous familial hypercholesterolemia with stenosis of the left anterior descending coronary artery successfully treated with weekly low‐density lipoprotein apheresis for 16 years without percutaneous coronary intervention
Authors: Yasu Takanori , Shimoyama Masahiro , Wada Hiroshi , Iwakura Tomohiro , Toyoda Shigeru , Kawabe Atsuhiko , Sugiyama Takushi
Published: July 2019

We successfully treated a patient with homozygous familial hypercholesterolemia (HoFH) with stable coronary arterial disease using optimal medical therapy and low‐density lipoprotein (LDL) apheresis for 16 years without percutaneous coronary intervention or bypass surgery. Intensive LDL lowering using apheresis and medication protected the patient from coronary atherosclerotic progression even in HoFH.
Sintering Resistance of Pt@SiO2 Core‐Shell Catalyst
Authors: Kim Seunghyun , Lee Siwon , Jung WooChul
Published: July 2019

Although core‐shell catalysts have been actively studied for their excellent stability at high temperatures, most studies have focused on the development of synthetic methods and not conducted actual catalytic reactions at conditions, under which particles severely agglomerate. Here, we prepare a model catalyst with a well‐defined size and interface of a Pt core and a gas‐permeable SiO2 shell via advanced colloidal synthesis, and evaluate the catalytic response to CO and CH4 oxidation, each representing low (<300 °C) and high (>500 °C) temperature reactions. Compared to typical SiO2 supported Pt, the core‐shell configuration shows comparable activity at CO oxidation and a much higher activity and stability for CH4 oxidation. However, even for the core‐shell, degradation is inevitable, and possible reasons for this are discussed. These practical results on high‐temperature catalysis provide important evaluation criteria and design guidelines for sintering‐resistant nanocatalysts.
In‐situ Growth of a Bimetallic Cobalt‐Nickel Organic Framework on Iron Foam: Achieving the Electron Modification on a Robust Self‐supported Oxygen Evolution Electrode
Authors: Luo Pei , Li Shixiong , Zhao Yasi , Ye Guojie , Wei Cong , Hu Yun , Wei Chaohai
Published: July 2019

As a clean energy source, hydrogen may be obtained via overall water splitting. However, the reaction is limited by the anodic oxygen evolution reaction (OER) in the catalytic field. In order to overcome the limitation in OER catalyst activity, this paper attempts to synthesize and develop a series of three‐dimensional metal‐organic frameworks (MOFs) electrocatalytic materials. The structure and morphology of bimetallic cobalt and nickel MOFs are characterized by FT‐IR, Raman, SEM, TEM, and XPS. It is found that the bimetallic cobalt and nickel MOFs have a columnar micro‐structure assembled by nanosheets. Further in‐situ growth on the iron (Fe) foam to prepare an integrated nanoarray self‐supported electrode did not significant change their micro‐structure. The obtained bimetal electrocatalysts exhibit significantly enhanced OER activity as compared to the single‐metal MOFs counterpart. The cobalt and nickel double‐doped materials in‐situ grown on Fe foam exhibited an excellent electrocatalytic activity and remarkable durability with a current density of 10 mA cm−2 in a 0.1 M KOH solution (with the overpotential of 264 mV and the Tafel slope of 54.3 mV dec−1). There is a significant improvement compared with the material on the glassy carbon electrode. The introduction of the bimetal species (Co and Ni) into the ordered MOFs provides a synergistic effect of the active centers resulting in an enhanced electron transfer and improved electrochemical performance. This work enriches the MOFs electrocatalytic electrode and pave the way for their practical applications.
Molecular Precursors for Tailoring Humidity Tolerance of Nanoscale Hopcalite Catalysts Via Flame Spray Pyrolysis
Authors: Wegner Karl , Zippel Rene , Medicus Maximilian , Schade Elke , Grothe Julia , Kaskel Stefan
Published: July 2019

A systematic investigation of copper‐ and manganese‐carboxylate precursors derived from various organic acids (arylcarboxylate, alkylcarboxyate) and their transformation into copper manganese nanoparticles via flame spray pyrolysis (FSP) reveals significant impact on their physical and catalytic properties. A sodium‐free protocol is essential to achieve high purity copper(II) and manganese(II) 2‐ethylhexanoates, benzoates, 1‐naphthenates and 9‐ anthracenates as revealed by infrared spectroscopy (IR) and thermogravimetry (TG). In order to exclude the influence of other parameters, the FSP syntheses were carried out using fixed air/feed ratio. Especially aromatic precursors lead to smaller nanoparticles with high surface areas up to 180 m2g−1 and that these also have a higher carbon content. TPR investigations have shown that the copper and manganese atoms are in close contact with each other, which significantly reduces their reduction temperature. In catalytic CO oxidation, all samples synthesized from organometallic precursors have shown higher CO conversions at room temperature under dry conditions and improved long‐term stability under wet conditions compared to a commercial reference. The activity depends mainly on the Cu : Mn ratio and the specific surface area. At room temperature under dry conditions, catalytic CO conversion exceeding 80 % could be achieved. A decreased deactivation rate under humid conditions could be related to an increased carbon content of the nanocatalysts. By optimization of the synthesis parameters and the use of pure precursors, it was possible to show that flame spray pyrolysis is an efficient, scalable and single‐stage synthesis method for Hopcalite nanoparticles, which additionally provides more active catalysts than those from alternative synthesis methods.
Nickel Exsolution‐Driven Phase Transformation from an n=2 to an n=1 Ruddlesden‐Popper Manganite for Methane Steam Reforming Reaction in SOFC Conditions
Authors: Vecino‐Mantilla Sebastián , Gauthier‐Maradei Paola , Huvé Marielle , Serra José Manuel , Roussel Pascal , Gauthier Gilles H.
Published: July 2019

An original way to perform the exsolution of Ni nanoparticles on a ceramic support was explored for the development of methane steam reforming catalyst in SOFC anode conditions. The n=2 Ruddlesden‐Popper (RP) phase La1.5Sr1.5Mn1.5Ni0.5O7±δ has been synthesized by the Pechini method and subsequently reduced with an H2‐N2 mixture at different temperatures and reducing times to induce the formation of two phases: LaSrMnO4 (n=1 RP) decorated with metallic Ni nanoparticles. Preliminary measurements of catalytic behavior for the steam reforming have been carried out in a reduction‐reaction process with a mixture of 82 mol %CH4, 18 mol %N2 and low steam to carbon ratio (S/C=0.15). The catalyst exhibits a selectivity for CO production (0.97), 14.60 mol % CH4 conversion and around 24.19 mol % H2 production. Such catalytic behavior was maintained for more than 4 h, with a constant rate of hydrogen production and CH4 conversion rate.
Bimetallic Synergy Effects of Phyllosilicate‐Derived NiCu@SiO2 Catalysts for 1,4‐Butynediol Direct Hydrogenation to 1,4‐Butanediol
Authors: Wang Changzhen , Tian Yani , Wu Ruifang , Li Haitao , Yao Benzhen , Zhao Yongxiang , Xiao Tiancun
Published: July 2019

Hydrogenation of 1,4‐butynediol (BYD) to 1,4‐butanediol (BDO) is a two‐step process, with an initial hydrogenation of BYD to 1,4‐butenediol (BED) and the subsequent hydrogenation of BED to BDO. However, the BYD hydrogenation also involves many side reactions originated from the isomerization of BED. In order to inhibit the isomerization pathways, phyllosilicate‐derived bimetallic NiCu@SiO2 catalysts have been developed for efficient C≡C/C=C hydrogenation in this work. Due to the formation of phyllosilicate matrix and highly dispersed metal nanoparticles, NiCu@SiO2 showed total BYD conversion with extremely high BDO selectivity compared to a conventional impregnated Ni/SiO2 catalyst. A remarkable result of NiCu@SiO2 catalysts is that a new type of bimetallic catalytic sites responsible for the high hydrogenation activity can be differentiated from the Ni phyllosilicate matrix by the induction of Cu species, and these neighboring bimetallic sites with the help of weak acid phyllosilicate interface, can realize to stabilize the activated BED species (allyl alcohol form) adsorbed on the cooperative active sites, thus to avoid its isomerization to aldehyde form and unexpected C=O hydrogenolysis. Consequently, it enhanced the selectivity to the diol products BDO significantly. Owing to the benign improvement of three center synergy effect, 9Ni1Cu@SiO2 possesses the optimum BYD direct hydrogenation ability with a rarely reported high selectivity of 90.5–94.5 % at 50 °C and 1 MPa.
Nitrogen‐Doped NiO Nanosheet Array for Boosted Electrocatalytic N2 Reduction
Authors: Wang Xiao‐hu , Wang Jing , Li Yu‐biao , Chu Ke
Published: July 2019

Electrocatalytic N2 reduction reaction (NRR) provides a sustainable approach for ambient N2 fixation. Non‐noble transition metal‐based electrocatalysts (TMEs) are emerging as the most promising NRR catalysts, but commonly exhibited limited NRR activity. Heteroatom doping is an effective method to improve the electrocatalytic activity of TMEs by finely modulating the electronic structures. Herein, as a proof‐of‐concept, nitrogen‐doped NiO nanosheet array on carbon cloth (N‐NiO/CC) was investigated as model heteroatom‐doped TMEs for NRR. The N‐NiO/CC exhibited the considerably enhanced NRR performance with a NH3 yield of 22.7 μg h−1 mg−1 and an FE of 7.3 % in 0.1 M LiClO4 at −0.5 V (vs. RHE), far superior to those of undoped counterpart. Density functional theory (DFT) calculations revealed that the N‐doping could induce the enhanced surface conductivity and upraised d‐band center, leading to promoted *NNH stabilization, reduced reaction energy barrier and thus improved NRR performance.
Model Studies on the Solid Electrolyte Interphase Formation on Graphite Electrodes in Ethylene Carbonate and Dimethyl Carbonate: Highly Oriented Pyrolytic Graphite
Authors: Weber Isabella , Schnaidt Johannes , Wang Bin , Diemant Thomas , Behm R. Jürgen
Published: July 2019

Aiming at a deeper understanding of the solid electrolyte interphase (SEI) formation on carbon anodes in lithium‐ion batteries, we performed a combined electrochemical and spectroscopic model study using structurally well‐defined graphite model electrodes (highly oriented pyrolytic graphite, HOPG) and simplified model electrolytes (ethylene carbonate (EC)+1 M LiPF6 or dimethyl carbonate (DMC)+1 M LiPF6). In cyclic voltammetry measurements, we find initial activation of the reductive electrolyte decomposition at faster scan rates (1 or 10 mV s−1), whereas this is not the case at a slower scan rate (0.1 mV s−1). This activation effect, which is more pronounced for DMC, is explained by an increase in the HOPG surface area, presumably by electrode exfoliation; it is not observed on surface‐defect‐rich samples. XPS analysis shows that, regardless of the solvent and the scan rate, the SEI is mainly composed of LiF and only small amounts of solvent and other salt decomposition products.
Enantioselective synthesis of (R)‐Cinacalcet via cobalt‐catalysed asymmetric Negishi cross‐coupling
Authors: Sun Xiao , Wang Xueyang , Liu Feipeng , Gao Zidong , Bian Qinghua , Wang Min , Zhong Jiangchun
Published: July 2019

A novel enantioselective synthesis of (R)‐cinacalcet with 99% enantiomeric excesses (ee) has been achieved. The main strategies of the approach include a gram‐scale cobalt‐catalysed asymmetric cross‐coupling of racemic ester with arylzinc reagent, Hoffman‐type rearrangement of acidamide, the amidation of chiral amine, and improving the ee of chiral amide from 87% to 99% via recrystallization.
Nano‐Engineered Materials for Transparent Supercapacitors
Authors: Chen Jun , Wang Yizhou , Liu Wenhui , Ma Yanwen
Published: July 2019

Transparent supercapacitors are interesting for energy storage and management in future transparent electronics and have become an intriguing research topic at the interface of materials science, energy and electronics research. This minireview presents the recent progress in transparent supercapacitors, particularly the use of nano‐engineered materials to construct transparent electrodes. Focusing on the two key features of transparency and capacitance, we analyze the influences of nanostructures on the electrode and device performances, and present the outlook the future perspectives for transparent supercapacitors.
NiSe2 as Co‐Catalyst with CdS: Nanocomposites for High‐Performance Photodriven Hydrogen Evolution under Visible‐Light Irradiation
Authors: Du Shiwen , Li Chunhe , Lin Xiao , Xu Wangping , Huang Xiang , Xu Hu , Fang Pengfei
Published: July 2019

One‐dimensional NiSe2/CdS nanocomposites (NCs), with NiSe2 nanoparticles (NPs) integrated onto the surface of CdS nanowires (NWs) were designed and fabricated through a two‐step in situ solvothermal method. Density functional theory (DFT) calculations showed that NiSe2 plays an important role in enhancing photocatalystic hydrogen (H2) production when coupled with CdS catalyst, which arises from 1) the contribution of Ni 3d and Se 4p orbitals to the electronic structures and 2) the charge redistribution at the interface region of the heterostructure results in efficient promotion of the charge transfer and separation of the photogenerated electron‐hole pairs. Under visible‐light illumination (λ≥400 nm), the NCs showed improved photocatalytic H2‐generation activity in the presence of lactic acid. The peak value of 7610.1 μmol h−1 g−1 for H2 production was achieved with an apparent quantum efficiency (AQE) of 41.68 % when the Ni/Cd ratio was set to 10 %, which was approximately 48 times higher than that of bare CdS NWs. Photoelectrochemical measurements also confirmed the pivotal role of NiSe2 in the improvement of the H2‐evolution performance of NiSe2/CdS NCs, which is consistent with the DFT investigations.
Cleavable Unimolecular Photoinitiators Based on Oxime‐Ester Chemistry for Two‐Photon Three‐Dimensional Printing
Authors: Qiu Wanwan , Hu Peng , Zhu Junzhe , Liu Ren , Li Zhiquan , Hu Zhiyong , Chen Qidai , Dietliker Kurt , Liska Robert
Published: July 2019

The development of efficient two‐photon initiators (2PIs) is critical to promote two‐photon three‐dimensional (3D) printing for market applications. On the basis of the photocleavage concept, several unimolecular 2PIs that contain coumarin moieties (as two‐photon absorption chromophores) and oxime‐ester groups (as initiation functional groups) were synthesized. Under visible light irradiation, the investigated oxime‐esters, sensitive to a broad wavelength range from 400 to 460 nm, undergo direct photocleavage followed by decarboxylation, forming active free radicals to effectively induce polymerization. Interestingly, the photoinitiators exhibit good photobleaching properties, which makes them applicable for photopolymerization of thick materials and dental restorative materials. In two‐photon 3D printing tests with acrylate formulations, the oxime‐ester derivatives were used to build complex 3D microstructures with submicrometer or even nanometer spatial resolution. The initiator comprised of a conjugated coumarin and an oxime ester attached at the 3‐position exhibited a low threshold laser power required for polymerization and had a broad processing window similar to a highly efficient 2PI in the literature.
NiFe Hydroxide Supported on Hierarchically Porous Nickel Mesh as a High‐Performance Bifunctional Electrocatalyst for Water Splitting at Large Current Density
Authors: Wang Pei‐can , Wan Lei , Lin Yu‐qun , Wang Bao‐guo
Published: July 2019

The preparation of efficient and low‐cost bifunctional catalysts with superior stability for water splitting is a topic of significant current interest for hydrogen generation. A facile strategy has been developed to fabricate highly active electrodes with hierarchical porous structures by using a two‐step electrodeposition method, in which NiFe layered double hydroxide is grown in situ on a three‐dimensional hierarchical Ni mesh (NiFe/Ni/Ni). The as‐prepared NiFe/Ni/Ni electrodes demonstrate remarkable structural stability with high surface areas, effective gas transportation, and fast electron transfer. Benefiting from the unique structure, the self‐supported NiFe/Ni/Ni electrodes exhibit overpotentials of 190 mV and 300 mV for the oxygen evolution reaction (OER) at current densities of 10 and 500 mA cm−2, respectively. Furthermore, the self‐supported NiFe/Ni/Ni electrodes also exhibit high performance in the hydrogen evolution reaction (HER) and excellent stability at a current density of 500 mA cm−2 for both OER and HER. Remarkably, using NiFe/Ni/Ni as both the cathode and anode for alkaline water electrolysis, a current density of 500 mA cm−2 is attained at a cell voltage of 1.96 V. Additionally, the water electrolyzer demonstrates superior stability even at a large current density (500 mA cm−2) when subjected to high temperatures.
Mesoporous Carbon with Different Density of Thiophenic‐Like Functional Groups and Their Effect on Oxygen Reduction
Authors: Brandiele Riccardo , Zerbetto Mirco , Dalconi Maria Chiara , Rizzi Gian Andrea , Isse Abdirisak Ahmed , Durante Christian , Gennaro Armando
Published: July 2019

The metal–support interactions between sulfur‐doped carbon supports (SMCs) and Pt nanoparticles (NPs) were investigated, aiming at verifying how sulfur functional groups can improve the electrocatalytic performance of Pt NPs towards the oxygen reduction reaction (ORR). SMCs were synthetized, tailoring the density of sulfur functional groups, and Pt NPs were deposited by thermal reduction of Pt(acac)2. The extent of the metal–support interaction was proved by X‐ray photoelectron spectroscopy (XPS) analysis, which revealed a strong electronic interaction, proportional to the density of sulfur defects, whereas XRD spectra provided evidence of higher strain in Pt NPs loaded on SMC. DFT simulations confirmed that the metal–support interaction was strongest in the presence of a high density of sulfur defects. The combination of microstrain and electronic effects resulted in a high catalytic activity of supported Pt NPs towards ORR, with linear correlations of the half‐wave potential E1/2 or the kinetic current jk with the sulfur content in the support. Furthermore, a mass activity value (550 A g−1) well above the United States Department of Energy target of 440 A g−1 at 0.9 V (vs. reversible hydrogen electrode, RHE), was determined.
Is reproductive strategy a key factor in understanding the evolutionary history of Southern Ocean Asteroidea (Echinodermata)?
Authors: Moreau Camille , Danis Bruno , Jossart Quentin , Eléaume Marc , Sands Chester , Achaz Guillaume , Agüera Antonio , Saucède Thomas
Published: July 2019

Life traits such as reproductive strategy can be determining factors of species evolutionary history and explain the resulting diversity patterns. This can be investigated using phylogeographic analyses of genetic units. In this work, the genetic structure of five asteroid genera with contrasting reproductive strategies (brooding: Diplasterias, Notasterias and Lysasterias versus broadcasting: Psilaster and Bathybiaster) was investigated in the Southern Ocean. Over 1,400 mtDNA cytochrome C oxidase subunit I (COI) sequences were analysed using five species delineation methods (ABGD, ASAP, mPTP, sGMYC and mGMYC), two phylogenetic reconstructions (ML and BA), and molecular clock calibrations, in order to examine the weight of reproductive strategy in the observed differences among phylogeographic patterns. We hypothesised that brooding species would show higher levels of genetic diversity and species richness along with a clearer geographic structuring than broadcasting species. In contrast, genetic diversity and species richness were not found to be significantly different between brooders and broadcasters, but broadcasters are less spatially structured than brooders supporting our initial hypothesis and suggesting more complex evolutionary histories associated to this reproductive strategy. Broadcasters' phylogeography can be explained by different scenarios including deep‐sea colonisation routes, bipolarity or cosmopolitanism, and sub‐Antarctic emergence for the genus Bathybiaster; Antarctic‐ New Zealand faunal exchanges across the Polar Front for the genus Psilaster. Brooders' phylogeography could support the previously formulated hypothesis of a past trans‐Antarctic seaway established between the Ross and the Weddell seas during the Plio‐Pleistocene. Our results also show, for the first time, that the Weddell Sea is populated by a mixed asteroid fauna originating from both the East and West Antarctic.
Conversion of rainforest to oil palm and rubber plantations alters energy channels in soil food webs
Authors: Susanti Winda Ika , Pollierer Melanie M. , Widyastuti Rahayu , Scheu Stefan , Potapov Anton
Published: July 2019

In the last decades, lowland tropical rainforest has been converted in large into plantation systems. Despite the evident changes above ground, the effect of rainforest conversion on the channeling of energy in soil food webs was not studied. Here, we investigated community‐level neutral lipid fatty acid profiles in dominant soil fauna to track energy channels in rainforest, rubber, and oil palm plantations in Sumatra, Indonesia. Abundant macrofauna including Araneae, Chilopoda, and Diplopoda contained high amounts of plant and fungal biomarker fatty acids (FAs). Lumbricina had the lowest amount of plant, but the highest amount of animal‐synthesized C20 polyunsaturated FAs as compared to other soil taxa. Mesofauna detritivores (Collembola and Oribatida) contained high amounts of algal biomarker FAs. The differences in FA profiles between taxa were evident if data were analyzed across land‐use systems, suggesting that soil fauna of different size (macro‐ and mesofauna) are associated with different energy channels. Despite that, rainforest conversion changed the biomarker FA composition of soil fauna at the community level. Conversion of rainforest into oil palm plantations enhanced the plant energy channel in soil food webs and reduced the bacterial energy channel; conversion into rubber plantations reduced the AMF‐based energy channel. The changes in energy distribution within soil food webs may have significant implications for the functioning of tropical ecosystems and their response to environmental changes. At present, these responses are hard to predict considering the poor knowledge on structure and functioning of tropical soil food webs.
Contrasting responses of steppe Stipa ssp. to warming and precipitation variability
Authors: Lv Xiaomin , He Qijin , Zhou Guangsheng
Published: July 2019

Climate change, characterized by warming and precipitation variability, restricted the growth of plants in arid and semiarid areas, and various functional traits are impacted differently. Comparing responses of functional traits to warming and precipitation variability and determining critical water threshold of dominate steppe grasses from Inner Mongolia facilitates the identification and monitoring of water stress effects. A combination of warming (ambient temperature, +1.5°C and +2.0°C) and varying precipitation (−30%, −15%, ambient, +15%, and +30%) manipulation experiments were performed on four Stipa species (S. baicalensis, S. bungeana, S. grandis, and S. breviflora) from Inner Mongolia steppe. The results showed that the functional traits of the four grasses differed in their responses to precipitation, but they shared common sensitive traits (root/shoot ratio, R/S, and specific leaf area; SLA) under ambient temperature condition. Warming increased the response of the four grasses to changing precipitation, and these differences in functional traits resulted in changes to their total biomass, with leaf area, SLA, and R/S making the largest contributions. Critical water thresholds of the four grasses were identified, and warming led to their higher optimum precipitation requirements. The four steppe grasses were able to adapt better to mild drought (summer precipitation decreased by 12%–28%) when warming 1.5°C rather than 2.0°C. These results indicated that if the Paris Agreement to limit global warming to 1.5°C will be accomplished, this will increase the probability for sustained viability of the Stipa steppes in the next 50–100 years.
Stoichiometry and daily rhythms: experimental evidence shows nutrient limitation decouples N uptake from photosynthesis
Authors: Chamberlin Catherine A. , Bernhardt Emily S. , Rosi Emma J. , Heffernan James B.
Published: July 2019

Diel variability in nutrient concentrations is common but not universal in aquatic ecosystems. Theoretical models of photoautotrophic systems attribute the absence of diel uptake variation to nutrient scarcity, such that diel variability in nutrient uptake disappears as nutrients become limiting. We tested this prediction in a mesocosm experiment, by exposing benthic algal communities to a range of nitrogen (N) and phosphorus concentrations and recording the rates of uptake during both day and night. We found that higher concentrations of N produced diel variability in uptake and that the difference between the day and night total mass uptakes approximately equaled N demand for observed primary production as seen in other studies. At lower concentrations of N, uptake rates during the day and night were indistinguishable. These results are the first empirical evidence to imply that diel nitrate patterns in streams and rivers indicate a release from N limitation and offer a new way to assess nutrient limitation.
Lewis Acidic Behavior of MoOF4 towards the Alkali Metal Fluorides in Anhydrous Hydrogen Fluoride Solutions
Authors: Stene Riane E. , Scheibe Benjamin , Karttunen Antti J. , Petry Winfried , Kraus Florian
Published: July 2019

Previous studies performed on samples of MoOF4 dissolved in anhydrous hydrogen fluoride (aHF) solutions have indicated the presence of the [Mo2O2F9]– anion. Building upon this earlier work, MoOF4, and MF (M = Li–Cs) were dissolved in aHF solutions to produce M[Mo2O2F9] (M = Li–Cs) salts. Structural analysis of the obtained compounds was performed using single‐crystal X‐ray diffraction. This study provides the first single crystal structures for the [MoVI2O2F9]– anion. Additionally, IR and Raman spectroscopy were used to characterize each salt. These spectra were compared to calculated ones for the solid‐state structure of each salt using the DFT‐PBE0 density functional method. The calculated spectra were used to give band assignments in the experimentally obtained spectra.
Retracted: Copper‐Catalyzed Decarboxylative C(sp2)‐C(sp3) and C(sp)‐C(sp3) Coupling of Substituted Cinnamic Acids and 3‐Phenyl Propiolic Acid with N‐Tosyl Oxaziridines
Authors: Nguyen Bich‐Ngoc , Cao Hai‐Thuong
Published: July 2019

The following article from the European Journal of Organic Chemistry, published online on 01 August 2019 in Wiley Online Library (https://chemistry‐europe.onlinelibrary.wiley.com/doi/full/10.1002/ejoc.201900982), has been retracted by agreement between the authors, Bich‐Ngoc Nguyen and Hai‐Thuong Cao, the journal's Editor‐in‐Chief, Anne Nijs, and Wiley‐VCH GmbH & Co. KGaA. The retraction has been agreed because the article had been submitted and approved for publication by Bich‐Ngoc Nguyen without consent by Keiji Maruoka under whose supervision the major part of the reported data was obtained.

A mild and efficient strategy for decarboxylative C(sp2)‐C(sp3) and C(sp)‐C(sp3) coupling of α,β‐unsaturated carboxylic acids such as substituted cinnamic acids and 3‐phenyl propiolic acid with N‐Tosyl oxaziridines was developed. The corresponding products were achieved in moderate to good yields with excellent stereoselectivity. Base‐free and oxidant‐free conditions allow good functional group tolerance. Radical inhibitors such as TEMPO and BHT completely suppressed the reactions suggesting a radical mechanism was involved. This study is supposed to broaden the frontier of oxaziridines' chemistry and to open up a novel cascade for alkylating reagents.
La2O3‐Promoted Ni/Al2O3 Catalyst for CO Methanation: Enhanced Catalytic Activity and Stability
Authors: Zhang Tengfei , Ai Hongmei , Liu Qing
Published: July 2019

To simultaneously inhibit Ni sintering and coke formation, while maintaining high catalytic activity, Ni–La2O3/Al2O3 catalysts are prepared by a modified deposition–precipitation (DP) method and applied for the CO methanation reaction. The activity of the catalyst prepared by the DP method is much higher than those prepared by the traditional impregnation and co‐impregnation methods due to the promotion of La2O3 as well as its unique dispersion on the surface of the catalyst. In the 100 h‐lifetime test under the conditions of 450 °C, 0.1 MPa, a weight hourly space velocity (WHSV) of 120 000 mL g−1 h−1, the Ni–La2O3/Al2O3 catalyst prepared by the DP method shows high catalytic stability. The characterization results show that La2O3 species can be deposited on the surface of the catalyst during the preparation process and can act as a physical barrier to prevent sintering of Ni particles and coke formation during high‐temperature reduction and reaction. La2O3 species can improve the reducibility of Ni particles and decrease the Ni particle sizes, resulting in larger H2 uptake and higher catalytic activity. Furthermore, the La3+/La2+ redox can also decrease coke formation by increasing the active oxygen species on the Ni surface.
Developmental tuning of mineralization drives morphological diversity of gill cover bones in sculpins and their relatives
Authors: Cytrynbaum Eli G. , Small Clayton M. , Kwon Ronald Y. , Hung Boaz , Kent Danny , Yan Yi-Lin , Knope Matthew L. , Bremiller Ruth A. , Desvignes Thomas , Kimmel Charles B.
Published: July 2019

The role of osteoblast placement in skeletal morphological variation is relatively well understood, but alternative developmental mechanisms affecting bone shape remain largely unknown. Specifically, very little attention has been paid to variation in later mineralization stages of intramembranous ossification as a driver of morphological diversity. We discover the occurrence of specific, sometimes large, regions of nonmineralized osteoid within bones that also contain mineralized tissue. We show through a variety of histological, molecular, and tomographic tests that this “extended” osteoid material is most likely nonmineralized bone matrix. This tissue type is a significant determinant of gill cover bone shape in the teleostean suborder Cottoidei. We demonstrate repeated evolution of extended osteoid in Cottoidei through ancestral state reconstruction and test for an association between extended osteoid variation and habitat differences among species. Through measurement of extended osteoid at various stages of gill cover development in species across the phylogeny, we gain insight into possible evolutionary developmental origins of the trait. We conclude that this fine-tuned developmental regulation of bone matrix mineralization reflects heterochrony at multiple biological levels and is a novel mechanism for the evolution of diversity in skeletal morphology. This research lays the groundwork for a new model in which to study bone mineralization and evolutionary developmental processes, particularly as they may relate to adaptation during a prominent evolutionary radiation of fishes.
Changes in the bioactive properties of strawberries caused by the storage in oxygen‐ and carbon dioxide‐enriched atmospheres
Authors: Van de Velde Franco , Esposito Debora , Overall John , Méndez‐Galarraga María Paula , Grace Mary , Élida Pirovani María , Lila Mary Ann
Published: July 2019

The changes in the antioxidant capacity, anti‐inflammatory, and wound healing properties of strawberry fruits as a consequence of the storage in atmospheres enriched in oxygen and carbon dioxide were investigated. Berries were exposed to two different gas compositions: 70% O2 + 20% CO2 and 90% O2 + 10% CO2, and stored for up to 20 days at 5°C. The antioxidant capacity, assessed through DPPH and FRAP methods, decreased around 17% in samples exposed to 70% O2 + 20% CO2 at day 20. However, the antioxidant activity of fruits stored in 90% O2 + 10% CO2 was maintained until day 20 and experienced an increase of around 10% on day 10. Moreover, strawberry stored in 90% O2 + 10% CO2 at days 5–10 showed an improved suppression of the pro‐inflammatory genes Cox‐2 and iNOS up to 30% higher than samples at day 0 in an in vitro LPS‐stimulated RAW 264.7 macrophage culture. In addition, berries exposed to 90% O2 + 10% CO2 at day 10 showed a human dermal fibroblast migration 30% higher than samples at day 0 in an in vitro skin‐fibroblast‐migration model. Therefore, evidence suggests that strawberry storage in 90% O2 + 10% CO2 can be a promissory alternative to offer fruits with enhanced bioactivity.
Physicochemical and microbiological characteristics of kitoza, a traditional salted/dried/smoked meat product of Madagascar
Authors: Ratsimba Angela , Rakoto Danielle , Jeannoda Victor , Andriamampianina Herizo , Talon Régine , Leroy Sabine , Grabulos Joël , Arnaud Elodie
Published: July 2019

Kitoza samples collected from producers in Madagascar were analyzed for their physicochemical and microbial properties. Lactic acid bacteria and coagulase‐negative staphylococci were the two codominant populations with average counts of 6–7 log cfu/g. Good hygienic practices were sometimes lacking but samples were not contaminated with Salmonella, Clostridium perfringens, and Bacillus cereus and only once with Listeria monocytogenes. Staphylococcus aureus was found occasionally with higher counts in salted/dried products than in salted/smoked products. Moisture, protein, fat, and salt contents varied considerably and were on average 41.5, 43.5, 14.3, and 3.3 g/100 g, respectively, and water activity was 0.893 on average. Smoked kitoza showed higher moisture content compared to dried kitoza. Most of the smoked kitoza had a water activity higher than 0.9 which is not in accordance with their storage at ambient temperatures. Benzo(a)pyrene content was above 2 µg/kg in 11 out of 30 smoked samples (17 ± 16.5 µg/kg on average).