bluuebunny/crossref_metadata_2025 huggingface dataset:
Increased produce enrichment reduces trauma in socially‐housed captive rhesus macaques (Macaca mulatta)
Authors: Wooddell Lauren J. , Beisner Brianne , Hannibal Darcy L. , Nathman Amy C. , McCowan Brenda
Published: November 2019

Due to primate adaptations for sociality, captive rhesus macaques have optimal welfare and utility as a biomedical model when they can be maintained in outdoor social groups. As a despotic species; however, aggression can result in costly injuries and may result in temporary or permanent removal of specific individuals from social housing. Enrichment items, such as toys, climbing structures, and foraging material, are employed to keep captive animals occupied. We hypothesized that produce enrichment that requires more processing to extract may reduce socially‐derived injuries by keeping animals occupied. We tested the effects of additional weekly produce (corn‐in‐husk, whole melon, or whole squash) on trauma incidence in an outdoor social group of rhesus macaques across two distinct seasons (mating and birthing seasons) at the California National Primate Research Center. Aggression and status behavioral data, food resource use and proximity, and trauma incidence were collected over two 16‐week periods, with eight control and treatment conditions alternating biweekly. Mixed‐effects regression modeling was used to determine the best predictors of trauma risk and severe aggression at the group level and at an individual level. We found that food resource use was an important predictor of trauma risk at both group and individual levels; greater use of food resources reduced trauma risk. Produce enrichment did not; however, reduce severe aggression. We suggest that other captive social groups of rhesus macaques with high levels of trauma may benefit from supplemental produce enrichment that increases animal engagement with food resources.
A 3.3 Å‐Resolution Structure of Hyperthermophilic Respiratory Complex III Reveals the Mechanism of Its Thermal Stability
Authors: Zhu Guoliang , Zeng Hui , Zhang Shuangbo , Juli Jana , Pang Xiaoyun , Hoffmann Jan , Zhang Yan , Morgner Nina , Zhu Yun , Peng Guohong , Michel Hartmut , Sun Fei
Published: November 2019

Respiratory chain complexes convert energy by coupling electron flow to transmembrane proton translocation. Owing to a lack of atomic structures of cytochrome bc1 complex (Complex III) from thermophilic bacteria, little is known about the adaptations of this macromolecular machine to hyperthermophilic environments. In this study, we purified the cytochrome bc1 complex of Aquifex aeolicus, one of the most extreme thermophilic bacteria known, and determined its structure with and without an inhibitor at 3.3 Å resolution. Several residues unique for thermophilic bacteria were detected that provide additional stabilization for the structure. An extra transmembrane helix at the N‐terminus of cyt. c1 was found to greatly enhance the interaction between cyt. b and cyt. c1, and to bind a phospholipid molecule to stabilize the complex in the membrane. These results provide the structural basis for the hyperstability of the cytochrome bc1 complex in an extreme thermal environment.
Transforming Porous Organic Cages into Porous Ionic Liquids via a Supramolecular Complexation Strategy
Authors: Jie Kecheng , Onishi Nicole , Schott Jennifer A. , Popovs Ilja , Jiang De‐en , Mahurin Shannon , Dai Sheng
Published: November 2019

Porous liquids are a type of porous materials that engineer permanent porosity into unique flowing liquids, exhibiting promising functionalities for a variety of applications. Here a Type I porous liquid is synthesized by transforming porous organic cages into porous ionic liquids via a supramolecular complexation strategy. Simple physical mixing of 18‐crown‐6 with task‐specific anionic porous organic cages affords a porous ionic liquid with anionic porous organic cages as the anionic parts and 18‐crown‐6/potassium ion complexes as the cationic parts. In contrast, mixing of 15‐crown‐5 and anionic porous organic cages in a 2:1 ratio gives only solids, while the addition of excess 15‐crown‐5 affords a Type II porous liquid. The permanent porosity in the cage‐based porous liquids has been also confirmed by molecular simulation, positron (e+) annihilation lifetime spectroscopy, and enhanced gas sorption capacity compared with pure crown ethers.
Enantioselective Synthesis of Multisubstituted Allenes by Cooperative Cu/Pd‐Catalyzed 1,4‐Arylboration of 1,3‐Enynes
Authors: Liao Yang , Yin Xuemei , Wang Xihong , Yu Wangzhi , Fang Dongmei , Hu Lianrui , Wang Min , Liao Jian
Published: November 2019

A cooperative Cu/Pd‐catalyzed enantioselective synthesis of multisubstituted allenes is established. By employing chiral sulfoxide phosphine (SOP)/Cu and PdCl2(dppf) complexes as catalysts, the 1,4‐arylboration of 1,3‐enynes provides an efficient approach to trisubstituted chiral allenes with up to 92 % yield and 97:3 er. Furthermore, by using 2‐substituted 1,3‐enynes as substrates, the tetrasubstituted chiral allenes were successfully generated using this strategy. Finally, theoretical calculations indicate that the transmetallation of the allenylcopper species is the rate‐limiting step of this transformation.
Organic–Inorganic Copolymerization for a Homogenous Composite without an Interphase Boundary
Authors: Yu Yadong , Mu Zhao , Jin Biao , Liu Zhaoming , Tang Ruikang
Published: November 2019

Ionic oligomers and their crosslinking implies a possibility to produce novel organic–inorganic composites by copolymerization. Using organic acrylamide monomers and inorganic calcium phosphate oligomers as precursors, uniformly structured polyacrylamide (PAM)‐calcium phosphate copolymer is prepared by an organic–inorganic copolymerization. In contrast to the previous PAM‐based composites by mixing inorganic components into polymers, the copolymerized material has no interphase boundary owing to the homogenous incorporation of the organic and inorganic units at molecular level, resulting in a complete and continuous hybrid network. The participation of the ionic binding effect in the crosslinking process can substantially improve the mechanical strength; the copolymer can reach a modulus and hardness of 35.14±1.91 GPa and 1.34±0.09 GPa, respectively, which are far superior to any other PAM‐based composites.
Developing Luminescent Ratiometric Thermometers Based on a Covalent Organic Framework (COF)
Authors: Kaczmarek Anna M. , Liu Ying‐Ya , Kaczmarek Mariusz K. , Liu Hengshuo , Artizzu Flavia , Carlos Luís D. , Van Der Voort Pascal
Published: November 2019

Covalent Organic Frameworks (COFs), an emerging class of crystalline porous materials, are proposed as a new type of support for grafting lanthanide ions (Ln3+) and employing these hybrid materials as ratiometric luminescent thermometers. A TpBpy‐COF—prepared from 1,3,5‐triformylphloroglucinol (Tp) and 2,2′‐bipyridine‐5,5′‐diamine (Bpy) grafted with Eu/Tb and Dy acetylacetone (acac) complexes can be successfully used as a luminescent thermometer in the 10–360 K (Eu) and 280–440 K (Tb) ranges with good sensing properties (thermal sensitivity up to 1.403 % K−1, temperature uncertainty δT<1 K above 110 K). For the Eu/Tb systems, we observe an unusual and rarely reported behavior, that is, no thermal quenching of the Tb3+ emission, a result of the absence of ion‐to‐ligand/host energy back‐transfer. The LnCOF materials proposed here could be a new class of materials employed for temperature‐sensing applications following up on the well‐known luminescent metal–organic framework thermometers.
High‐Resolution Electrochemical Mapping of the Hydrogen Evolution Reaction on Transition‐Metal Dichalcogenide Nanosheets
Authors: Takahashi Yasufumi , Kobayashi Yu , Wang Ziqian , Ito Yoshikazu , Ota Masato , Ida Hiroki , Kumatani Akichika , Miyazawa Keisuke , Fujita Takeshi , Shiku Hitoshi , Korchev Yuri E. , Miyata Yasumitsu , Fukuma Takeshi , Chen Mingwei , Matsue Tomokazu
Published: November 2019

High‐resolution scanning electrochemical cell microscopy (SECCM) is used to image and quantitatively analyze the hydrogen evolution reaction (HER) catalytically active sites of 1H‐MoS2 nanosheets, MoS2, and WS2 heteronanosheets. Using a 20 nm radius nanopipette and hopping mode scanning, the resolution of SECCM was beyond the optical microscopy limit and visualized a small triangular MoS2 nanosheet with a side length of ca. 130 nm. The electrochemical cell provides local cyclic voltammograms with a nanoscale spatial resolution for visualizing HER active sites as electrochemical images. The HER activity difference of edge, terrace, and heterojunction of MoS2 and WS2 were revealed. The SECCM imaging directly visualized the relationship of HER activity and number of MoS2 nanosheet layers and unveiled the heterogeneous aging state of MoS2 nanosheets. SECCM can be used for improving local HER activities by producing sulfur vacancies using electrochemical reaction at the selected region.
Yellow Circularly Polarized Luminescence from C1‐Symmetrical Copper(I) Complexes
Authors: Deng Min , Mukthar Nishya F. M. , Schley Nathan D. , Ung Gaël
Published: November 2019

The synthesis of chiral C1‐symmetrical copper(I) complexes supported by chiral carbene ligands is described. These complexes are yellow emitters with modest quantum yields. Circularly polarized luminescence (CPL) spectra show a polarized emission band with dissymmetry factors |glum|=1.2×10−3. These complexes are the first reported examples of molecular copper(I) complexes exhibiting circularly polarized luminescence. In contrast with most CPL‐emitting molecules, which possess either helical or axial chirality, the results presented show that simple chiral architectures are suitable for CPL emission and unlock new synthetic possibilities.
Ultrasound‐assisted nanoscaled supramolecular coordination polymer as an efficient recyclable catalyst for photocatalytic degradation of dye pollutants
Authors: Etaiw Safaa Eldin H. , Fayed Tarek A. , Abd El‐Aziz Dina M. , Khatab Hayam M.
Published: November 2019

An ultrasound‐assisted nanoscaled supramolecular coordination polymer (nanosized 1′) has been synthesized using a self‐assembly reaction of K3[Cu (CN)4] and hexamethylenetetramine in the presence of Me3SnCl under ambient conditions. Nanosized1′ was examined using elemental analysis, Fourier transform–infrared, transmission electron microscopy, scanning electron microscopy and X‐ray powder diffractions. It was structurally compared with the single crystal supramolecular coordination polymer ∞3[Cu6(CN)7(C6H12N4)2(OH3)]; SCP 1. The photocatalytic activities of nanosized 1′ and SCP 1 toward different hazardous organic dyes were determined under ambient, UV‐light irradiation and ultrasonic conditions. SCP 1 and nanosized 1′ as heterogeneous nanoparticles catalysts exhibited high catalytic activity for degradation of Congo Red, Methyl Violet 2B and Methylene Blue dyes. The effects of operational parameters on catalytic degradation process, identification of the degradation products and recycling of the catalyst were also investigated. SCP 1 and nanosized 1′ are recyclable heterogeneous catalysts and can be reused with efficient activities. The mechanism of degradation using different scavenger techniques iss proposed and discussed. The catalytic oxidation process is mainly caused by •OH radicals.
Polydimethylsiloxane/monomer casting nylon copolymers: Preparation, flame‐retardant properties, and wear‐resistant properties
Authors: Song Ling , Yang Haiyang , Li Duxin , Jiang Qibin , Zeng Dan
Published: November 2019

In order to improve the toughness, wear resistance, and combustion properties of the monomer casting nylon (MC nylon) materials, the polydimethylsiloxane (PDMS) segment is bonded to the nylon molecular chain by copolymerization. PDMS/MC nylon copolymers are prepared via in situ anionic polymerization with macro‐activator based on PDMS terminated with hexamethylene diisocyanate. The effects of different macro‐activator content on the mechanical properties, water absorption, thermal stability, friction and wear properties, and combustion properties of the copolymers are characterized. The results show that the impact strength of the copolymer improves significantly (optimally increases by 2.6 times) and the water absorption rate decreases with the increase of PDMS content. The introduction of the silicon–oxygen structure reduces the peak heat release rate of copolymer materials (optimally decreases about 28.7%), while it promotes the decomposition of the system, resulting in a slight decrease in the thermal stability of the materials. Adding 5 wt % PDMS can decrease the wear loss of MC nylon from 6.2 mg of pure nylon to 1.6 mg. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48753.
The stability and antiapoptotic activity of Bm30K‐3 can be improved by lysine acetylation in the silkworm, Bombyx mori
Authors: Ma Yafei , Wu Chengcheng , Liu Jiahan , Liu Yue , Lv Jiao , Sun Zihan , Wang Dan , Jiang Caiying , Sheng Qing , You Zhengying , Nie Zuoming
Published: November 2019

Acetylation is an important, highly conserved, and reversible post‐translational modification of proteins. Previously, we showed by nano‐HPLC/MS/MS that many nutrient storage proteins in the silkworm are acetylated. Among these proteins, most of the known 30K proteins were shown to be acetylated, including 23 acetylated 30K proteins containing 49 acetylated sites (Kac), indicating the importance of the acetylation of 30K proteins in silkworm. In this study, Bm30K‐3, a 30K protein containing three Kac sites, was further assessed in functional studies of its acetylation. Increasing the level of Bm30K‐3 acetylation by adding the deacetylase inhibitor trichostatin A (TSA) increased the levels of this protein and further inhibited cellular apoptosis induced by H2O2. In contrast, decreasing the level of acetylation by adding the acetylase inhibitor C646 could reduce the level of Bm30K‐3 and increase H2O2‐induced apoptosis. Subsequently, BmN cells were treated with CHX and MG132, and increasing the acetylation level using TSA was shown to inhibit protein degradation and improve the stability of Bm30K‐3. Furthermore, the acetylation of Bm30K‐3 could compete with its ability to be ubiquitinated, suggesting that acetylation could inhibit the ubiquitin‐mediated proteasome degradation pathway, improving the stability and accumulation of proteins in cells. These results further indicate that acetylation might regulate nutrition storage and utilization in Bombyx mori, which requires further study.
Thermosetting Shape Memory Polymers and Composites Based on Polybenzoxazine Blends, Alloys and Copolymers
Authors: Mora Phattarin , Schäfer Hannes , Jubsilp Chanchira , Rimdusit Sarawut , Koschek Katharina
Published: November 2019

When dealing with smart polymers, in particular with shape memory polymers, the polymer type and composition specify the overall material properties and in particular the extent of the shape memory effect. Polybenzoxazines as a polymer with high potential for structural applications represent a promising component for materials with both shape memory effect and structurally interesting material properties. This minireview gives insight into how the shape memory effect, in particular the shape recovery event, is influenced by internal factors such as polymer structure, morphology and external factors such as filler addition.
Regulated Single‐Axis Rotations of a Carbonaceous Guest in a van der Waals Complex with an Entropy Cost
Authors: Matsuno Taisuke , Nakai Yusuke , Maniwa Yutaka , Someya Maki , Sato Sota , Isobe Hiroyuki
Published: November 2019

In a tight host–guest complex assembled solely by nondirectional van der Waals forces, unique motions of the guest, such as solid‐state inertial rotations, emerge. The regulation of dynamic motions is an important element to be explored for novel functions of such complexes, which may be seemingly difficult to achieve because of the nondirectionality of the assembling forces. A regulated, single‐axis rotation was made possible by choosing an appropriate shape of the guest in the tubular host. Specifically, an ellipsoidal guest was made to stand along a cylinder axis of the host, which consequently resulted in single‐axis rotations of the guest in the solid. The rotational frequency was considerably high for solid‐state rotations but was suppressed to 10 GHz, which was 1/20 of the isotropic rotation of a spherical guest. In‐depth kinetic analyses quantitatively revealed that the entropy cost was a determining factor that regulated the dynamics.
A tutorial on dynamic risk prediction of a binary outcome based on a longitudinal biomarker
Authors: Dandis Rana , Teerenstra Steven , Massuger Leon , Sweep Fred , Eysbouts Yalck , IntHout Joanna
Published: November 2019

Dynamic risk predictions based on all available information are useful in timely identification of high‐risk patients. However, in contrast with time to event outcomes, there is still a lack of studies that clearly demonstrate how to obtain and update predictions for a future binary outcome using a repeatedly measured biomarker. The aim of this study is to give an illustrative overview of four approaches to obtain such predictions: likelihood based two‐stage method (2SMLE), likelihood based joint model (JMMLE), Bayesian two‐stage method (2SB), and Bayesian joint model (JMB). We applied the approaches to provide weekly updated predictions of post–molar gestational trophoblastic neoplasia (GTN) based on age and repeated measurements of human chorionic gonadotropin (hCG). Discrimination and calibration measures were used to compare the accuracy of the weekly predictions. Internal validation of the models was conducted using bootstrapping. The four approaches resulted in the same predictive and discriminative performance in predicting GTN. A simulation study showed that the joint models outperform the two‐stage methods when we increase the within‐ and the between‐patients variability of the biomarker. The applicability of these models to produce dynamic predictions has been illustrated through a comprehensive explanation and accompanying syntax (R and SAS®).
How individuals change during internet‐based interventions for depression: A randomized controlled trial comparing standardized and individualized feedback
Authors: Zagorscak Pavle , Heinrich Manuel , Bohn Johannes , Stein Jana , Knaevelsrud Christine
Published: November 2019

Background

Standardized and individualized Internet‐based interventions (IBI) for depression yield significant symptom improvements. However, change patterns during standardized or individualized IBI are unknown. Identifying subgroups that experience different symptom courses during IBI and their characteristics is vital for improving response.

Methods

Mildly to moderately depressed individuals according to self‐report (N = 1,089) were randomized to receive module‐wise feedback that was either standardized or individualized by a counselor within an otherwise identical cognitive‐behavioral IBI for depression (seven modules over six weeks). Depressive symptoms were assessed at baseline and before each module (Patient Health Questionnaire; PHQ‐9). Other individual characteristics (self‐report) and the presence of an affective disorder (structured clinical interview) were assessed at baseline. Growth mixture modeling was used to identify and compare subgroups with discernable change patterns and associated client variables across conditions.

Results

Model comparisons suggest equal change patterns in both conditions. Across conditions, a group of immediate (62.5%) and a group of delayed improvers (37.5%) were identified. Immediate improvers decreased their PHQ‐9 score by 5.5 points from pre to post, with 33% of improvement occurring before treatment commenced. Delayed improvers were characterized by stable symptom severity during the first two modules and smaller overall symptom decrease (3.4 points). Higher treatment expectations, a current major depressive disorder (interview), and lower social support were associated with delayed improvement.

Conclusion

Internet‐based interventions for depression with individualized and with standardized feedback lead to comparable patterns of change. Expectation management and bolstering of social support are promising strategies for individuals that are at risk for delayed improvement.
Introducing Excel spreadsheet calculations and numerical simulations with professional software into an undergraduate hydraulic engineering course
Authors: Bermúdez María , Puertas Jerónimo , Cea Luis
Published: November 2019

This paper presents a comprehensive set of computer tools for implementing an active teaching–learning strategy on an undergraduate hydraulic engineering course, within the subject blocks of pressure flow and free surface flow. The tools comprise a number of simple Excel‐based applications, to enhance students’ understanding of basic concepts, plus a series of practical exercises using the free professional models EPANET and IBER, aimed at familiarizing students with the tools used in real practice. The application of the new methodology to a hydraulics course at the Civil Engineering School of the University of A Coruña (Spain) resulted in increased student satisfaction and engagement, as well as greater interaction with instructors and classmates. The applications and practical exercises are easily adaptable and freely available to the community to facilitate their application to other courses and/or degrees.
Melatonin reverses the oxidative stress and mitochondrial dysfunction caused by LETM1 silencing
Authors: Aral Cenk , Demirkesen Seyma , Bircan Rıfat , Yasar Sirin Duygu
Published: November 2019

LETM1 is a mitochondrial inner‐membrane protein, which is encoded by a gene present in a locus of 4p, which, in turn, is deleted in the Wolf–Hirschhorn Syndrome, and is assumed to be related to its pathogenesis. The cellular damage caused by the deletion is presumably related to oxidative stress. Melatonin has many beneficial roles in protecting mitochondria by scavenging reactive oxygen species, maintaining membrane potential, and improving functions. The aim of this study was to investigate the effects of melatonin administration to LETM1‐silenced mouse embryonic fibroblast cells as a cellular model for LETM1 deficiency. We transfected mouse embryonic fibroblast cells with a pair of siRNA against LETM1 and monitored the oxidative stress and mitochondrial functions with or without melatonin addition. MnSOD expression and aconitase activity decreased and oxidized protein levels increased in LETM1‐silenced cells. LETM1 suppression did not alter the expression of OXPHOS complexes, but the oxygen consumption rates decreased significantly; however, this change was not related to complex I but instead involved complex IV and complex II. Melatonin supplementation effectively normalized the parameters studied, including the oxygen consumption rate. Our findings identified a novel effect of LETM1 deficiency on cellular respiration via complex II as well as a potential beneficial role of melatonin treatment. On the other hand, these effects may be specific to the cell line used and need to be verified in other cell lines.
Integrating Asexuality: A is for Asexual in LGBTQIA+
Authors: Teut Jo
Published: November 2019

This chapter addresses the large gap in information about asexual identities, examines potential prevalence rates of asexual individuals interacting with community colleges, and equips practitioners with tools for integrating asexuality into their current LGBTQIA+ initiatives.
Intravascular ultrasound radiofrequency signal analysis of blood speckles: Physiological assessment of intermediate coronary artery stenosis
Authors: Okada Kozo , Hibi Kiyoshi , Matsushita Kensuke , Yagami Hiroyuki , Tamura Kouichi , Honda Yasuhiro , Kimura Kazuo
Published: November 2019

Background

This study aimed to systematically investigate feasibility of radiofrequency intravascular ultrasound (RF‐IVUS) analysis of blood signals for assessing functionally significant coronary stenosis.

Methods

First, in‐vivo human study was performed to evaluate 83 intermediate coronary lesions from 75 patients, using 40‐MHz RF‐IVUS, fractional flow reserve (FFR) and instantaneous wave‐free ratio (iFR). Average blood integrated‐backscatter (IB) values within lumen were measured at proximal and distal segments to the stenosis; ΔIB values between the two sites were calculated. Second, bench‐test was performed to assess relationships of blood IB values to blood flow velocity and hematocrit using 40 and 60‐MHz RF‐IVUS.

Results

In in‐vivo study, ΔIB values across the stenosis significantly correlated with both FFR (r = −.85, p < .0001) and iFR (r = −.65, p < .0001), which was confirmed in small minimum lumen area (MLA) lesions (MLA <2.0 mm2). Receiver operating characteristic curve analyses identified the best cut‐off value as 10.06 of ΔIB values for predicting FFR ≤0.8 and iFR ≤0.89 (sensitivity 76.2 and 95.5%, specificity 100 and 82.0%, positive predictive value 100 and 65.6%, negative predictive value 80.4 and 98.0%, accuracy 92.9 and 92.8% for FFR and iFR). Bench‐test study also identified that blood IB values exponentially changed as a function of blood flow velocity at any given hematocrit in both 40 and 60‐MHz RF‐IVUS.

Conclusions

This study supports the potential utility of RF‐IVUS analysis of blood signals to estimate functional ischemia, demonstrating relationships of blood ΔIB values to FFR and iFR, as well as relationships between blood IB values and flow velocity.
Flash Catalytic Pyrolysis of Polyethylene over (Alumino)silicate Materials
Authors: Klaimy Sophie , Ciotonea Carmen , Dhainaut Jérémy , Royer Sébastien , Casetta Mathilde , Duquesne Sophie , Tricot Grégory , Lamonier Jean‐François
Published: November 2019

A series of amorphous and crystalline (alumino)silicate catalysts, with variable acidity, are evaluated for the flash pyrolysis of polyethylene (PE). Catalysts morphology, acidity as well as textural properties are influencing the process of decomposition of PE. Incomplete PE conversion and significant wax formation are obtained under the reaction condition with pure amorphous and MFI‐type silica. Complete conversion, and limited formation of wax, are observed with amorphous and MFI‐type Si−Al containing catalyst. Acidity has a significant influence on the molecule size and nature. Then, the increase of the catalyst acidity leads to the decrease of the molecular weight of pyrolysis products and the increase of the gas and the light liquid fractions. In addition, the acidity increase promotes cyclization reaction, resulting in the increase of the cycled hydrocarbon/aromatic proportion in the liquid fraction. Then, from PE catalytic pyrolysis, up to 25 wt.% of aromatics can be obtained in the liquid fraction with Si/Al ZSM‐5 zeolite, while olefins remain the major fraction with the less acidic amorphous aluminosilicate catalyst.
Vanadium Doped Nickel Phosphide Nanosheets Self‐Assembled Microspheres as a High‐Efficiency Oxygen Evolution Catalyst
Authors: Li Yao , Jiang Xiaoli , Miao Zhuang , Tang Jiaruo , Zheng Qiaoji , Xie Fengyu , Lin Dunmin
Published: November 2019

Recently, much attention has been paid to the low‐cost, high‐efficiency and stable non‐precious metal catalysts for oxygen evolution reaction (OER). In this work, vanadium (V)‐doped nickel phosphide (Ni2P) nanosheets self‐assembled microspheres supported on nickel foam (Ni1V1P NSs/NF) were synthesized as a novel OER catalyst by combined processes of hydrothermal method and low‐temperature phosphorization. The synthesized Ni1V1P NSs/NF material shows excellent catalytic activity due to its interconnected three‐dimensional (3D) structure and synergistic effect between nickel and vanadium. When used as a catalyst electrode for OER, the synthesized Ni1V1P NSs/NF exhibits excellent electrocatalytic activity, reaching a current density of 50 mA cm−2 at the low overpotential of 250 mV in 1.0 M KOH. This material also shows superior electrochemical stability with negligible decay of the activity after continual measurement for 15 h at 50 and 100 mA cm−2 in 1.0 M KOH, respectively. This work provides a valuable method to synthesize efficient OER catalysts by doping valence‐variable metal ions and designing distinctive 3D structure.
Tuning PtII‐Based Donor–Acceptor Systems through Ligand Design: Effects on Frontier Orbitals, Redox Potentials, UV/Vis/NIR Absorptions, Electrochromism, and Photocatalysis
Authors: Sobottka Sebastian , Nößler Maite , Ostericher Andrew L. , Hermann Gunter , Subat Noah Z. , Beerhues Julia , Behr‐van der Meer Margarethe , Suntrup Lisa , Albold Uta , Hohloch Stephan , Tremblay Jean Christophe , Sarkar Biprajit
Published: November 2019

Asymmetric platinum donor–acceptor complexes [(pimp)Pt(Q2−)] are presented in this work, in which pimp=[(2,4,6‐trimethylphenylimino)methyl]pyridine and Q2−=catecholate‐type donor ligands. The properties of the complexes are evaluated as a function of the donor ligands, and correlations are drawn among electrochemical, optical, and theoretical data. Special focus has been put on the spectroelectrochemical investigation of the complexes featuring sulfonyl‐substituted phenylendiamide ligands, which show redox‐induced linkage isomerism upon oxidation. Time‐dependent density functional theory (TD‐DFT) as well as electron flux density analysis have been employed to rationalize the optical spectra of the complexes and their reactivity. Compound 1 ([(pimp)Pt(Q2−)] with Q2−=3,5‐di‐tert‐butylcatecholate) was shown to be an efficient photosensitizer for molecular oxygen and was subsequently employed in photochemical cross‐dehydrogenative coupling (CDC) reactions. The results thus display new avenues for donor–acceptor systems, including their role as photocatalysts for organic transformations, and the possibility to introduce redox‐induced linkage isomerism in these compounds through the use of sulfonamide substituents on the donor ligands.
One Amine–3 Tasks: Reductive Coupling of Imines with Olefins in Batch and Flow
Authors: Lefebvre Quentin , Porta Riccardo , Millet Anthony , Jia Jiaqi , Rueping Magnus
Published: November 2019

Owing to their wide range of biological properties, γ‐aminobutyric acid derivatives (GABA) have been extensively studied and found noteworthy industrial applications. However, atom‐economical and efficient processes for their production are scarce and would greatly benefit from further investigations. Herein, we demonstrate that an iridium‐based photocatalyst promotes the direct reductive cross‐coupling of imines with olefins upon irradiation with visible light to give GABA derivatives in good yields and selectivities. We also stress the enabling triple role of tributylamine additive in this process, discuss the advantages of strategies based on proton‐coupled electron transfer (PCET) and demonstrate the scale‐up of this reaction in continuous flow.
Ligand‐Mediated Regioselective Rhodium‐Catalyzed Benzotriazole–Allene Coupling: Mechanistic Exploration and Quantum Chemical Analysis
Authors: Sergeieva Tetiana , Hamlin Trevor A. , Okovytyy Sergiy , Breit Bernhard , Bickelhaupt F. Matthias
Published: November 2019

The ligand‐controlled rhodium‐catalyzed regioselective coupling of 1,2,3‐benzotriazoles and allenes was investigated by DFT calculations. Because allylation can occur at either the N1 or N2 position of the 1,2,3‐benzotriazole, the complete Gibbs free energy profiles for both pathways were computed. A kinetic preference emerged for the experimentally observed N1 allylation with the JoSPOphos ligand, whereas N2 allylation was favored with DPEphos. Analysis of the regiodetermining oxidative addition step by using the activation strain model in conjunction with a matching energy decomposition analysis has revealed that the unprecedented N2 reaction regioselectivity is dictated by the strength of the electrostatic interactions between the 1,2,3‐benzotriazole and the rhodium catalyst. The nature of the electrostatic interaction was rationalized by analysis of the electrostatic potential maps and Hirshfeld charges: a stabilizing electrostatic interaction was found between the key atoms involved in the oxidative addition for the N2 pathway, analogous interactions are weaker in the N1 case.
Low‐dropout regulator with dual cross‐coupled current mirrors
Authors: Woo Yuet Ho , Leung Ka Nang , Zheng Yanqi , Guo Jianping
Published: November 2019

A low‐dropout regulator (LDO) based on dual cross‐coupled current mirrors is reported in this paper. The proposed dual cross‐coupled current mirrors boost output signal current such that the loop gain of LDO is significantly enhanced, and the error amplifier in LDO retains single‐pole property within the loop bandwidth of LDO. Designed in a 65‐nm CMOS process and operating at a minimum of 1‐V supply, the proposed LDO provides a 0.8‐V output and delivers a maximum of 50 mA. The figure‐of‐merit of the proposed LDO is 8.9 ps.
Synthesis, Crystal Structure, and Excellent Selective Pb2+ Ion Adsorption of New Layered Compound (NH4)In3(SO4)2(OH)6
Authors: Zhao Yu , Hu Keyan , Wang Dong , Zhang Shaoning , Wang Peng , Dong Wujie , Chen Haijie , Zhao Wei , Huang Fuqiang
Published: November 2019

(NH4)In3(SO4)2(OH)6, a new indium incorporated synthetic compound belonging to the alunite supergroup, is successfully prepared by hydrothermal reaction. The crystal structure is determined by single‐crystal X‐ray diffraction. (NH4)In3(SO4)2(OH)6 crystallizes in space group R3m of a = b = 7.69(8) Å, c = 17.71(2) Å and Z = 3, and it adopts a layered structure with alternating corrugated two‐dimensional 2∞[In3(SO4)2(OH)6–] anionic network and interstitial NH4+ ions. The measurements of X‐ray powder diffraction pattern, Fourier transform infrared spectroscopy spectrum, differential Scanning Calorimeter and X‐ray photoelectron spectroscopy have been performed on this new compound. The title compound is air‐ and water‐stable and starts thermal decomposition to In2O3 at 620 K. Interstitial NH4+ ions between two‐dimensional 2∞[In3(SO4)2(OH)6–] layers are exchangeable by cations like Pb2+. The maximum adsorption capacity of Pb2+ ions reaches 990 mg/g at pH 6.5, and the selectivity is observed with a very high distribution coefficient Kd of 1.1 × 106 mL/g compared with other completive cations. The unique layered framework composed of [InO6]9– octahedra and [SO4]2– tetrahedra is chemically stable to enable excellent cycling performance. This investigation will advocate the alunite supergroup minerals for efficient and recyclable adsorption of toxic metal ions in contaminated water.
Diastereoselective sp3‐C–H Functionalization of Arylmethyl Ketones and Transformation of E‐ to Z‐Products Through Photocatalysis
Authors: Rastogi Gaurav K. , Deka Bhaskar , Deb Mohit L. , Baruah Pranjal K.
Published: November 2019

We have developed an efficient metal‐free route for the synthesis of 1,4‐enedione derivatives under microwave irradiation by reacting easily available arylmethylketones with DMSO or diphenyl sulfoxide in the presence of TBAI and persulfate. The reaction is very clean and completes within very short time. All the reagents and catalysts are cheap and environmentally benign. In addition, the E‐isomer of the products can easily be transformed into the Z‐isomer by using eosin Y photocatalyst under the irradiation of white CFL.
Determination of S‐adenosylmethionine, S‐adenosylhomocysteine, and methylthioadenosine in urine using solvent‐modified micellar electrokinetic chromatography
Authors: Ivanov Alexander Vladimirovich , Kruglova Mariya Petrovna , Virus Edward Danielevich , Bulgakova Polina Olegovna , Vital'evich Grachev Sergei , Kubatiev Aslan Amirkhanovich
Published: November 2019

A new approach for direct determination of S‐adenosylmethionine (SAM), S‐adenosylhomocysteine (SAH), and methylthioadenosine (MTA) in urine was developed based on MEKC by using SDS modified with isobutanol in the presence of PEG‐300. Analytes were first extracted with grafted phenylborononic acid. Using a 50 µm internal diameter silica capillary of 32 cm total length filled with 0.05 M SDS, 0.05 M H3PO4, 5% (v/v) isobutanol, and 10% (v/v) PEG‐300, LOQ of 0.15 µM for SAM and SAH, and 0.2 µM for MTA was reached. Accuracy was 92% for MTA, 109% for SAH, and 105% for SAM, intra‐ and interday imprecision were <2.5 and ≤3%, respectively. The total time of analysis for one sample was 10 min. Analysis of 30 urine samples from healthy volunteers showed that the median SAM and SAH levels were 12.1 and 0.73 µM, respectively. MTA levels, which were determined in urine for the first time (according to our data), were 0.43 µM, and these values correlated well with the SAM level (r = 0.748, p < 0.01).
Holocene paleogeographic evolution of an ancient port city of the central Mediterranean area: Natural and anthropogenic modifications from Salerno city, southern Italy
Authors: Amato Vincenzo , Aiello Giuseppe , Barra Diana , Caporaso Lucia , Caruso Tonino , Giaccio Biagio , Parisi Roberta  , Rossi Amedeo
Published: November 2019

A multidiplisciplinary study, including geomorphological, lithostratigraphical, geochronological, geochemical, and paleontological investigations, was carried out in the coastal area of Salerno city, southern Italy. The study aimed to outline the Late Glacial‐Holocene geoenvironmental evolution of Salerno's port area in response to both natural and anthropogenic factors. The geomorphological study included an examination of historic maps, which enabled a detailed reconstruction of the coastal landscape change during historic times. Lithostratigraphical analyses of three new boreholes, supported by radiocarbon and tephrochronological data, and of previously retrieved core‐successions and archaeological trenches, extends our reconstruction of the paleogeographical evolution of the Salerno coastal area back to the Late Pleistocene. Geochemical and paleontological analyses of samples from the newly acquired cores were combined with the lithofacies analyses of previously retrieved cores to detect ancient harbors in the area of the current port facilities of the city and surrounding urban areas. This work contributes to scientific debate about the specific sedimentary architectures and geochemical properties of the Salerno harbor environment and refines methodological approaches for characterizing and assessing the evolution and demise of ancient port facilities in Mediterranean coastal cities.
White matter hyperintensities mediate gray matter volume and processing speed relationship in cognitively unimpaired participants
Authors: Brugulat‐Serrat Anna , Salvadó Gemma , Operto Grégory , Cacciaglia Raffaele , Sudre Carole H. , Grau‐Rivera Oriol , Suárez‐Calvet Marc , Falcon Carles , Sánchez‐Benavides Gonzalo , Gramunt Nina , Minguillon Carolina , Fauria Karine , Barkhof Frederik , Molinuevo José L. , Gispert Juan D. ,   ALFA Study
Published: November 2019

White matter hyperintensities (WMH) have been extensively associated with cognitive impairment and reductions in gray matter volume (GMv) independently. This study explored whether WMH lesion volume mediates the relationship between cerebral patterns of GMv and cognition in 521 (mean age 57.7 years) cognitively unimpaired middle‐aged individuals. Episodic memory (EM) was measured with the Memory Binding Test and executive functions (EF) using five WAIS‐IV subtests. WMH were automatically determined from T2 and FLAIR sequences and characterized using diffusion‐weighted imaging (DWI) parameters. WMH volume was entered as a mediator in a voxel‐wise mediation analysis relating GMv and cognitive performance (with both EM and EF composites and the individual tests independently). The mediation model was corrected by age, sex, education, number of Apolipoprotein E (APOE)‐ε4 alleles and total intracranial volume. We found that even at very low levels of WMH burden in the cohort (median volume of 3.2 mL), higher WMH lesion volume was significantly associated with a widespread pattern of lower GMv in temporal, frontal, and cerebellar areas. WMH mediated the relationship between GMv and EF, mainly driven by processing speed, but not EM. DWI parameters in these lesions were compatible with incipient demyelination and axonal loss. These findings lead to the reflection on the relevance of the control of cardiovascular risk factors in middle‐aged individuals as a valuable preventive strategy to reduce or delay cognitive decline.
Endothelial Bone Morphogenetic Protein 2 (Bmp2) Knockout Exacerbates Hemochromatosis in Homeostatic Iron Regulator (Hfe) Knockout Mice but not Bmp6 Knockout Mice
Authors: Xiao Xia , Dev Som , Canali Susanna , Bayer Abraham , Xu Yang , Agarwal Aneesh , Wang Chia‐Yu , Babitt Jodie L.
Published: November 2019

Background and Aims

Bone morphogenetic proteins BMP2 and BMP6 play key roles in systemic iron homeostasis by regulating production of the iron hormone hepcidin. The homeostatic iron regulator (HFE) also regulates hepcidin through a mechanism that intersects with the BMP–mothers against decapentaplegic homolog 1/5/8 (SMAD1/5/8) pathway. However, the relative roles of BMP2 compared with BMP6 and whether HFE regulates hepcidin through a BMP2‐dependent mechanism remain uncertain.

Approach and Results

We therefore examined the iron phenotype of mice deficient for both Bmp2 and Bmp6 or both Bmp2 and Hfe compared with single knockout (KO) mice and littermate controls. Eight‐week‐old double endothelial Bmp6/Bmp2 KO mice exhibited a similar degree of hepcidin deficiency, serum iron overload, and tissue iron overload compared with single KO mice. Notably, dietary iron loading still induced liver SMAD5 phosphorylation and hepcidin in double Bmp6/endothelial Bmp2 KO mice, although no other BMP ligand mRNAs were increased in the livers of double KO mice, and only Bmp6 and Bmp2 mRNA were induced by dietary iron loading in wild‐type mice. In contrast, double Hfe/endothelial Bmp2 KO mice exhibited reduced hepcidin and increased extrahepatic iron loading compared to single Hfe or endothelial Bmp2 KO mice. Liver phosphorylated SMAD5 and the SMAD1/5/8 target inhibitor of DNA binding 1 (Id1) mRNA were also reduced in double Hfe/endothelial Bmp2 KO compared with single endothelial Bmp2 KO female mice. Finally, hepcidin and Id1 mRNA induction by homodimeric BMP2, homodimeric BMP6, and heterodimeric BMP2/6 were blunted in Hfe KO primary hepatocytes.

Conclusions

These data suggest that BMP2 and BMP6 work collaboratively to regulate hepcidin expression, that BMP2‐independent and BMP6‐independent SMAD1/5/8 signaling contributes a nonredundant role to hepcidin regulation by iron, and that HFE regulates hepcidin at least in part through a BMP2‐independent but SMAD1/5/8‐dependent mechanism.
Effect of using plastic nanofuel as a fuel in a light‐duty diesel engine
Authors: Kaimal Viswanath K. , Vijayabalan P. , Balachandar M. , Padmanaba Sundar S. , Sathyamurthy Ravishankar
Published: November 2019

A novel nanofuel is formulated using aluminum oxide (alumina) nanoparticles (AONs) in neat plastic oil (PO). A light‐duty compression‐ignition engine is used in the present investigation to analyze the effect of a 100% plastic nanofuel under different concentrations of nanoparticle on performance, combustion, and emission characteristics. The modified fuels used for conducting the experiment were formulated by mixing PO with 100, 150, and 200 mg/L of AON. The results of the physical and chemical properties of neat PO were significantly improved, in addition to AON. The nanofuels exhibited lower in‐cylinder pressure, delay period, and combustion duration than that of neat PO operation. The performance analysis revealed a 10.3% increase in thermal efficiency for PAN200 nanofuel compared with PO and it was almost the same as that of conventional diesel fuel. The emission levels of HC, CO, and smoke for PO‐based nanofuels were reduced significantly at all brake mean effective pressure values, whereas the reduction in the NOX emission was only marginal. At full load, the emission of smoke, HC and CO of the PAN200 nanofuel were lower than the diesel operation. Overall, the engine fueled with nanofuel exhibited superior characteristics compared to that of neat PO operation.
Does the common law power to grant cross‐border insolvency assistance apply to an insolvency winding‐up that is voluntary? The reaction to Singularis from Singapore and Hong Kong
Authors: Qu Charles Zhen , Godwin Andrew
Published: November 2019

In many common law jurisdictions, the common law power of courts to grant assistance in respect of foreign insolvency proceedings exists independently of statute. The nature of the power, however, continues to generate debate. Obiter dicta of the Privy Council suggests that no assistance is available where the foreign proceeding is a voluntary winding‐up. This article evaluates the position by reference to Singapore and Hong Kong decisions and concludes that a refusal to grant assistance in circumstances involving an insolvent voluntary winding‐up is inconsistent with the principle of modified universalism and that a broader recognition test should be adopted.
Effect of the levonorgestrel‐releasing intrauterine system on cardiovascular risk markers among women with thrombophilia or previous venous thromboembolism
Authors: Braga Giordana C. , Brito Milena B. , Ferriani Rui A. , Oliveira Luciana C. , Garcia Andrea A. , Pintão Maria C. , Vieira Carolina S.
Published: November 2019

Objective

To assess the effects of the levonorgestrel‐releasing intrauterine system (LNG‐IUS) on standard cardiovascular risk markers among women with thrombophilia and/or previous venous thromboembolism (VTE).

Methods

A prospective cohort study enrolled women aged 18–45 years with thrombophilia and/or a history of VTE who received the 52‐mg LNG‐IUS (20 μg/d initial release) at the University of Ribeirão Preto Medical School, Brazil, from January 2006 to December 2015. Before and 12 months after LNG‐IUS placement, the following cardiovascular risk markers were assessed: lipid profile, body mass index (BMI), blood glucose, systolic blood pressure, diastolic blood pressure, and waist circumference. The primary outcome was changes in cardiovascular risk markers. A subanalysis of anticoagulant users versus non‐users was also conducted.

Results

In total, 45 women were enrolled. BMI increased by 2.3% after 12 months of LNG‐IUS placement (P < 0.01), but the other risk factors did not change. Cardiovascular risk markers were similar between anticoagulant users and non‐users after 12 months of LNG‐IUS use.

Conclusion

Among women with thrombophilia and/or previous VTE, cardiovascular risk markers were not found to change significantly after 12 months of LNG‐IUS use. The study adds safety information regarding use of the LNG‐IUS for women at risk of thromboembolism.
Nanoscale control of grain boundary potential barrier, dopant density and filled trap state density for higher efficiency perovskite solar cells
Authors: Bahrami Behzad , Mabrouk Sally , Adhikari Nirmal , Elbohy Hytham , Gurung Ashim , Reza Khan M. , Pathak Rajesh , Chowdhury Ashraful H. , Saianand Gopalan , Yue Wenjin , Zai Jiantao , Qian Xuefeng , Liang Mao , Qiao Qiquan
Published: November 2019

In this work, grain boundary (GB) potential barrier (
Δφ
GB), dopant density (Pnet), and filled trap state density (PGB,trap) were manipulated at the nanoscale by exposing the fabricated perovskite films to various relative humidity (RH) environments. Spatial mapping of surface potential in the perovskite film revealed higher positive potential at GBs than inside the grains. The average
Δφ
GB, Pnet, and PGB,trap in the perovskite films decreased from 0% RH to 25% RH exposure, but increased when the RH increased to 35% RH and 45% RH. This clearly indicated that perovskite solar cells fabricated at 25% RH led to the lowest average GB potential, smallest dopant density, and least filled trap states density. This is consistent with the highest photovoltaic efficiency of 18.16% at 25% RH among the different relative humidities from 0% to 45% RH.

image