bluuebunny/crossref_metadata_2025 huggingface dataset:
Lightning Forcing in Global Fire Models: The Importance of Temporal Resolution
Authors: Felsberg A. , Kloster S. , Wilkenskjeld S. , Krause A. , Lasslop G.
Published: December 2017

In global fire models, lightning is typically prescribed from observational data with monthly mean temporal resolution while meteorological forcings, such as precipitation or temperature, are prescribed in a daily resolution. In this study, we investigate the importance of the temporal resolution of the lightning forcing for the simulation of burned area by varying from daily to monthly and annual mean forcing. For this, we utilize the vegetation fire model JSBACH‐SPITFIRE to simulate burned area, forced with meteorological and lightning data derived from the general circulation model ECHAM6. On a global scale, differences in burned area caused by lightning forcing applied in coarser temporal resolution stay below 0.55% compared to the use of daily mean forcing. Regionally, however, differences reach up to 100%, depending on the region and season. Monthly averaged lightning forcing as well as the monthly lightning climatology cause differences through an interaction between lightning ignitions and fire prone weather conditions, accounted for by the fire danger index. This interaction leads to decreased burned area in the boreal zone and increased burned area in the Tropics and Subtropics under the coarser temporal resolution. The exclusion of interannual variability, when forced with the lightning climatology, has only a minor impact on the simulated burned area. Annually averaged lightning forcing causes differences as a direct result of the eliminated seasonal characteristics of lightning. Burned area is decreased in summer and increased in winter where fuel is available. Regions with little seasonality, such as the Tropics and Subtropics, experience an increase in burned area.
A new kernel RLS algorithm for systems with bounded noise
Authors: Constantin I. , Constantin J. , Bigand A.
Published: December 2017

In this paper, we propose a new nonlinear set‐membership recursive least‐squares algorithm. The algorithm draws on a linear set‐membership filter in conjunction with kernels for nonlinear processing. Set‐membership algorithms exploit a priori model information that directly, or indirectly, prescribes dynamic constraints on the solution space. Such information is disregarded by conventional approaches. Kernel methods provide an implicit mapping of the data in a high‐dimensional feature space where linear techniques are applied. Computations are done in the initial space by means of kernel functions. In this work, we develop a kernel‐based version of a set‐membership filter that belongs to a class of optimal bounding ellipsoid algorithms. Optimal bounding ellipsoid algorithms compute ellipsoidal approximations to regions in the parameter space that are consistent with the observed data and the model assumptions. Experiments involving stationary and nonstationary data are presented. Compared with existing kernel adaptive algorithms, the proposed algorithm offers an enhanced performance and sparsity, conjugated with better tracking capabilities.
On the need of projections in input‐error model reference adaptive control
Authors: Barabanov Nikita , Ortega Romeo
Published: December 2017

The main objective of this note is to contribute, if modestly, toward the understanding of the input‐error model reference adaptive control scheme revealing an instability mechanism that arises if the projection of the plant high‐frequency gain coefficient estimate is omitted. In addition, a self‐contained proof of global convergence of the scheme with the projections for a simple first‐order plant is given.
Toward Stretchable Self‐Powered Sensors Based on the Thermoelectric Response of PEDOT:PSS/Polyurethane Blends
Authors: Taroni Prospero J. , Santagiuliana Giovanni , Wan Kening , Calado Philip , Qiu Manting , Zhang Han , Pugno Nicola M. , Palma Matteo , Stingelin‐Stutzman Natalie , Heeney Martin , Fenwick Oliver , Baxendale Mark , Bilotti Emiliano
Published: December 2017

The development of new flexible and stretchable sensors addresses the demands of upcoming application fields like internet‐of‐things, soft robotics, and health/structure monitoring. However, finding a reliable and robust power source to operate these devices, particularly in off‐the‐grid, maintenance‐free applications, still poses a great challenge. The exploitation of ubiquitous temperature gradients, as the source of energy, can become a practical solution, since the recent discovery of the outstanding thermoelectric properties of a conductive polymer, poly(3,4‐ethylenedioxythiophene)‐poly(styrenesulfonate) (PEDOT:PSS). Unfortunately the use of PEDOT:PSS is currently constrained by its brittleness and limited processability. Herein, PEDOT:PSS is blended with a commercial elastomeric polyurethane (Lycra), to obtain tough and processable self‐standing films. A remarkable strain‐at‐break of ≈700% is achieved for blends with 90 wt% Lycra, after ethylene glycol treatment, without affecting the Seebeck voltage. For the first time the viability of these novel blends as stretchable self‐powered sensors is demonstrated.
Selective Surface Enhanced Raman Scattering for Quantitative Detection of Lung Cancer Biomarkers in Superparticle@MOF Structure
Authors: Qiao Xuezhi , Su Bensheng , Liu Cong , Song Qian , Luo Dan , Mo Guang , Wang Tie
Published: December 2017

Surface enhanced Raman scattering (SERS) is a trace detection technique that extends even to single molecule detection. Its potential application to the noninvasive recognition of lung malignancies by detecting volatile organic compounds (VOCs) that serve as biomarkers would be a breakthrough in early cancer diagnostics. This application, however, is currently limited by two main factors: (1) most VOC biomarkers exhibit only weak Raman scattering; and (2) the high mobility of gaseous molecules results in a low adsorptivity on solid substrates. To enhance the adsorption of gaseous molecules, a ZIF‐8 layer is coated onto a self‐assembly of gold superparticles (GSPs) in order to slow the flow rate of gaseous biomarkers and depress the exponential decay of the electromagnetic field around the GSP surfaces. Gaseous aldehydes that are released as a result of tumor‐specific tissue composition and metabolism, thereby acting as indicators of lung cancer, are guided onto SERS‐active GSPs substrates through a ZIF‐8 channel. Through a Schiff base reaction with 4‐aminothiophenol pregrafted onto gold GSPs, gaseous aldehydes are captured with a 10 ppb limit of detection, demonstrating tremendous prospects for in vitro diagnoses of early stage lung cancer.
Controllable Solid Electrolyte Interphase in Nickel‐Rich Cathodes by an Electrochemical Rearrangement for Stable Lithium‐Ion Batteries
Authors: Kim Junhyeok , Lee Jieun , Ma Hyunsoo , Jeong Hu Young , Cha Hyungyeon , Lee Hyomyung , Yoo Youngshin , Park Minjoon , Cho Jaephil
Published: December 2017

The layered nickel‐rich materials have attracted extensive attention as a promising cathode candidate for high‐energy density lithium‐ion batteries (LIBs). However, they have been suffering from inherent structural and electrochemical degradation including severe capacity loss at high electrode loading density (>3.0 g cm−3) and high temperature cycling (>60 °C). In this study, an effective and viable way of creating an artificial solid–electrolyte interphase (SEI) layer on the cathode surface by a simple, one‐step approach is reported. It is found that the initial artificial SEI compounds on the cathode surface can electrochemically grow along grain boundaries by reacting with the by‐products during battery cycling. The developed nickel‐rich cathode demonstrates exceptional capacity retention and structural integrity under industrial electrode fabricating conditions with the electrode loading level of ≈12 mg cm−2 and density of ≈3.3 g cm−3. This finding could be a breakthrough for the LIB technology, providing a rational approach for the development of advanced cathode materials.
Single‐Site AuI Catalyst for Silane Oxidation with Water
Authors: Chen Zheng , Zhang Qi , Chen Wenxing , Dong Juncai , Yao Hurong , Zhang Xiangbo , Tong Xuanjue , Wang Dingsheng , Peng Qing , Chen Chen , He Wei , Li Yadong
Published: December 2017

Single‐site Au anchored on mpg‐C3N4 (519 ppm Au loading) is developed as a highly active, selective, and stable catalyst for the oxidation of silanes with water with a turnover frequency as high as 50 200 h−1, far exceeding most known catalysts based on total gold content. Other hydrosilanes bearing unsaturated functional groups also lead to corresponding silanols under mild reaction conditions without formation of any side products in good or excellent yields. The spherical aberration correction electron microscopy and extended X‐ray absorption fine structure measurements both confirm the atomic dispersion of Au atoms stabilized by mpg‐C3N4. The coordination of the catalytically active AuI by three nitrogen or carbon atoms in the tri‐s‐triazine repeating units not only prevents the Au atoms from aggregation, but also renders the surface AuI highly active, which is completely different than homogeneous AuI species.
Titanium Disulfide Coated Carbon Nanotube Hybrid Electrodes Enable High Energy Density Symmetric Pseudocapacitors
Authors: Zang Xining , Shen Caiwei , Kao Emmeline , Warren Roseanne , Zhang Ruopeng , Teh Kwok Siong , Zhong Junwen , Wei Minsong , Li Buxuan , Chu Yao , Sanghadasa Mohan , Schwartzberg Adam , Lin Liwei
Published: December 2017

While electrochemical supercapacitors often show high power density and long operation lifetimes, they are plagued by limited energy density. Pseudocapacitive materials, in contrast, operate by fast surface redox reactions and are shown to enhance energy storage of supercapacitors. Furthermore, several reported systems exhibit high capacitance but restricted electrochemical voltage windows, usually no more than 1 V in aqueous electrolytes. Here, it is demonstrated that vertically aligned carbon nanotubes (VACNTs) with uniformly coated, pseudocapacitive titanium disulfide (TiS2) composite electrodes can extend the stable working range to over 3 V to achieve a high capacitance of 195 F g−1 in an Li‐rich electrolyte. A symmetric cell demonstrates an energy density of 60.9 Wh kg−1—the highest among symmetric pseudocapacitors using metal oxides, conducting polymers, 2D transition metal carbides (MXene), and other transition metal dichalcogenides. Nanostructures prepared by an atomic layer deposition/sulfurization process facilitate ion transportation and surface reactions to result in a high power density of 1250 W kg−1 with stable operation over 10 000 cycles. A flexible solid‐state supercapacitor prepared by transferring the TiS2–VACNT composite film onto Kapton tape is demonstrated to power a 2.2 V light emitting diode (LED) for 1 min.
3D Mesoporous van der Waals Heterostructures for Trifunctional Energy Electrocatalysis
Authors: Tang Cheng , Zhong Ling , Zhang Bingsen , Wang Hao‐Fan , Zhang Qiang
Published: December 2017

The emergence of van der Waals (vdW) heterostructures of 2D materials has opened new avenues for fundamental scientific research and technological applications. However, the current concepts and strategies of material engineering lack feasibilities to comprehensively regulate the as‐obtained extrinsic physicochemical characters together with intrinsic properties and activities for optimal performances. A 3D mesoporous vdW heterostructure of graphene and nitrogen‐doped MoS2 via a two‐step sequential chemical vapor deposition method is constructed. Such strategy is demonstrated to offer an all‐round engineering of 2D materials including the morphology, edge, defect, interface, and electronic structure, thereby leading to robustly modified properties and greatly enhanced electrochemical activities. The hydrogen evolution is substantially accelerated on MoS2, while the oxygen reduction and evolution are significantly improved on graphene. This work provides a powerful overall engineering strategy of 2D materials for electrocatalysis, which is also enlightening for other nanomaterials and energy‐related applications.
Rechargeable Aqueous Zinc‐Ion Battery Based on Porous Framework Zinc Pyrovanadate Intercalation Cathode
Authors: Xia Chuan , Guo Jing , Lei Yongjiu , Liang Hanfeng , Zhao Chao , Alshareef Husam N.
Published: December 2017

In this work, a microwave approach is developed to rapidly synthesize ultralong zinc pyrovanadate (Zn3V2O7(OH)2·2H2O, ZVO) nanowires with a porous crystal framework. It is shown that our synthesis strategy can easily be extended to fabricate other metal pyrovanadate compounds. The zinc pyrovanadate nanowires show significantly improved electrochemical performance when used as intercalation cathode for aqueous zinc–ion battery. Specifically, the ZVO cathode delivers high capacities of 213 and 76 mA h g−1 at current densities of 50 and 3000 mA g−1, respectively. Furthermore, the Zn//ZVO cells show good cycling stability up to 300 cycles. The estimated energy density of this Zn cell is ≈214Wh kg−1, which is much higher than commercial lead–acid batteries. Significant insight into the Zn‐storage mechanism in the pyrovanadate cathodes is presented using multiple analytical methods. In addition, it is shown that our prototype device can power a 1.5 V temperature sensor for at least 24 h.
Peptide Integrated Optics
Authors: Handelman Amir , Lapshina Nadezda , Apter Boris , Rosenman Gil
Published: December 2017

Bio‐nanophotonics is a wide field in which advanced optical materials, biomedicine, fundamental optics, and nanotechnology are combined and result in the development of biomedical optical chips. Silk fibers or synthetic bioabsorbable polymers are the main light‐guiding components. In this work, an advanced concept of integrated bio‐optics is proposed, which is based on bioinspired peptide optical materials exhibiting wide optical transparency, nonlinear and electrooptical properties, and effective passive and active waveguiding. Developed new technology combining bottom‐up controlled deposition of peptide planar wafers of a large area and top‐down focus ion beam lithography provides direct fabrication of peptide optical integrated circuits. Finding a deep modification of peptide optical properties by reconformation of biological secondary structure from native phase to β‐sheet architecture is followed by the appearance of visible fluorescence and unexpected transition from a native passive optical waveguiding to an active one. Original biocompatibility, switchable regimes of waveguiding, and multifunctional nonlinear optical properties make these new peptide planar optical materials attractive for application in emerging technology of lab‐on‐biochips, combining biomedical photonic and electronic circuits toward medical diagnosis, light‐activated therapy, and health monitoring.
Nanocomposite Capacitors with Significantly Enhanced Energy Density and Breakdown Strength Utilizing a Small Loading of Monolayer Titania
Authors: Wen Rongmei , Guo Junmeng , Zhao Chunlin , Liu Yanqing
Published: December 2017

The dielectric capacitor with high electric energy density is demanded for modern electronic and electrical power systems. However, their energy density is considerably limited by a low dielectric constant and low breakdown strength. Here, thin flexible polymer nanocomposites with high energy density are obtained by only adding a small loading of 2D monolayer titania along with concurrent improvements of dielectric constant and breakdown strength. This work not only first reveals that monolayer titania is an excellent filler that can be comparable to existing fillers in nanocomposite capacitors but also provides a facile approach to thin flexible compact dielectric films with ultrahigh energy density and breakdown strength for energy storage applications.
Tailored Porous ZnCo2O4 Nanofibrous Electrocatalysts for Lithium–Oxygen Batteries
Authors: Kim Jae‐Chan , Lee Gwang‐Hee , Lee Seun , Oh Seung‐Ik , Kang Yongku , Kim Dong‐Wan
Published: December 2017

Lithium‐oxygen batteries are considered a next‐generation technology owing to their extremely high theoretical energy density despite many challenges such as low round‐trip efficiency and poor cyclability. The air‐cathode structure and pore properties play a key role in solving these problems. In this study, we fabricate ZnCo2O4 nanofibers and design a porous nanostructure using a facile electrospinning process and selective etching of ZnO as the cathode material in lithium‐oxygen batteries. First, non‐porous ZnCo2O4 nanofiber electrodes accomplish high catalytic activity and good cycling stability during 116 cycles with a limited capacity of 1000 mA h g−1 at a current density of 500 mA g−1. For enhanced catalytic activity and cyclability, ZnO included ZnCo2O4 nanofibers are prepared using a Zn‐excess electrospun solution and porous ZnCo2O4 nanofibers are fabricated via selective etching of ZnO. Porous ZnCo2O4 nanofiber electrodes exhibit excellent electrocatalytic activity and cyclability for 226 cycles with a limited capacity of 1000 mA h g−1 at a current density of 500 mA g−1. The exceptional catalytic properties explain the synergistic effect of the one‐dimensional nanostructure and porous structure with an appropriate pore diameter, providing a large active site and an efficient electron pathway during the Li2O2 formation/decomposition process.
Oxidant‐Mediated Nitrogenation and Recyclization of Imidazo[1,2‐a]pyridines with Sodium Azide: Synthesis of 4H‐Pyrido[1,2‐a][1,3,5]triazin‐4‐ones
Authors: Cao Gangjian , Chen Zhengkai , Song Jinyu , Xu Jianfeng , Miao Maozhong , Ren Hongjun
Published: December 2017

An expeditious and straightforward approach for the synthesis of 4H‐pyrido[1,2‐a][1,3,5]triazin‐4‐ones starting from readily available imidazo[1,2‐a]pyridines and sodium azide has been presented under aerobic oxidative conditions. The reaction proceeded well with the promotion of potassium persulfate/potassium permanganate with good functional group tolerance. A wide range of biologically valuable 4H‐pyrido[1,2‐a][1,3,5]triazin‐4‐one scaffolds were assembled by this methodology. The gram‐scale reaction was also achieved. A cascade nitrogenation and oxidative recyclization sequence could be involved in the reaction.

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Calcium Doping Facilitates Water Dissociation in Magnesium Oxide
Authors: Müller Danny , Knoll Christian , Ruh Thomas , Artner Werner , Welch Jan M. , Peterlik Herwig , Eitenberger Elisabeth , Friedbacher Gernot , Harasek Michael , Blaha Peter , Hradil Klaudia , Werner Andreas , Weinberger Peter
Published: December 2017

Calcium doping of magnesium oxide results in significantly increased water dissociation rates, thus enhancing both hydration rate and reaction completeness of hydration compared to pure MgO. For a series of mixed magnesium–calcium oxides (MgxCa1−xO) with varying Ca contents between 0% and 40%, the material of a composition Mg0.9Ca0.1O shows the fastest rehydration, transforming completely within 80 min to the mixed hydroxide. In consecutive dehydration/rehydration cycles, reasonable cycle stability is found. A “regeneration” of the aged material (reactivity reduced by excessive cycling) in liquid water re‐establishes the initial rehydration reactivity. Density functional theory calculations support the experimental findings, confirming that calcium doping can reduce the energy of the rate limiting water dissociation reaction, exploiting both electronic and steric (size) effects.
Nanoimaging of Electronic Heterogeneity in Bi2Se3 and Sb2Te3 Nanocrystals
Authors: Lu Xiaowei , Khatib Omar , Du Xutao , Duan Jiahua , Wei Wei , Liu Xianli , Bechtel Hans A. , D'Apuzzo Fausto , Yan Mingtao , Buyanin Alexander , Fu Qiang , Chen Jianing , Salmeron Miquel , Zeng Jie , Raschke Markus B. , Jiang Peng , Bao Xinhe
Published: December 2017

Topological insulators (TIs) are quantum materials with topologically protected surface states surrounding an insulating bulk. However, defect‐induced bulk conduction often dominates transport properties in most TI materials, obscuring the Dirac surface states. In order to realize intrinsic topological insulating properties, it is thus of great significance to identify the spatial distribution of defects, understand their formation mechanism, and finally control or eliminate their influence. Here, the electronic heterogeneity in polyol‐synthesized Bi2Se3 and chemical vapor deposition‐grown Sb2Te3 nanocrystals is systematically investigated by multimodal atomic‐to‐mesoscale resolution imaging. In particular, by combining the Drude response sensitivity of infrared scattering‐type scanning near‐field optical microscopy with the work‐function specificity of mirror electron microscopy, characteristic mesoscopic patterns are identified, which are related to carrier concentration modulation originating from the formation of defects during the crystal growth process. This correlative imaging and modeling approach thus provides the desired guidance for optimization of growth parameters, crucial for preparing TI nanomaterials to display their intrinsic exotic Dirac properties.
Age is a predictor of a small decrease in lung function in children with sickle cell anemia
Authors: Willen Shaina M. , Cohen Robyn , Rodeghier Mark , Kirkham Fenella , Redline Susan S. , Rosen Carol , Kirkby Jane , DeBaun Michael R.
Published: December 2017

The longitudinal pattern of lung function in children with sickle cell anemia (SCA) has shown a decrease in FEV1% predicted, a risk factor for death in adults with SCA, but predictors for this decline are poorly characterized. In a prospective longitudinal multi‐center cohort of children with SCA, we tested the hypotheses that: (1) FEV1% predicted declines over time; and (2) SCA‐specific characteristics and therapy predict this decline. At three clinical centers, children with SCA (HbSS or HbSβ0 thalassemia), unselected for respiratory disease, were enrolled in the Sleep and Asthma Cohort (SAC) study. Study‐certified pulmonary function technicians performed spirometry and lung volumes. Each assessment was reviewed centrally. Predicted values were determined for TLC, FEV1, FVC, and FEV1/FVC ratio. A total of 197 participants, mean age 11.0 years at first testing (range 4‐19.3 years), had a minimum of three spirometry measurements, over an average of 4.4 years (range 1.1‐6.5 years) from baseline to endpoint. In a multivariable model, FEV1% predicted declines by 0.3% for every additional year of age (95% CI −0.56 to −0.05, P = .020). Sex, asthma history, hemoglobin, reticulocyte count, white blood cell count, incidence rate of severe acute pain and acute chest syndrome episodes, and hydroxyurea therapy were not associated with a decline in FEV1% predicted. In a large, rigorously evaluated, prospective cohort of an unselected group of children with SCA, FEV1% predicted declines minimally over an average of 4 years, and none of the examined disease features predict the decline.
Similar outcome of allogeneic stem cell transplantation after myeloablative and sequential conditioning regimen in patients with refractory or relapsed acute myeloid leukemia: A study from the Société Francophone de Greffe de Moelle et de Thérapie Cellulaire
Authors: Decroocq Justine , Itzykson Raphaël , Vigouroux Stéphane , Michallet Mauricette , Yakoub‐Agha Ibrahim , Huynh Anne , Beckerich Florence , Suarez Felipe , Chevallier Patrice , Nguyen‐Quoc Stéphanie , Ledoux Marie‐Pierre , Clement Laurence , Hicheri Yosr , Guillerm Gaëlle , Cornillon Jérôme , Contentin Nathalie , Carre Martin , Maillard Natacha , Mercier Mélanie , Mohty Mohamad , Beguin Yves , Bourhis Jean‐Henri , Charbonnier Amandine , Dauriac Charles , Bay Jacques‐Olivier , Blaise Didier , Deconinck Eric , Jubert Charlotte , Raus Nicole , Peffault de Latour Regis , Dhedin Nathalie
Published: December 2017

Patients with acute myeloid leukemia (AML) in relapse or refractory to induction therapy have a dismal prognosis. Allogeneic hematopoietic stem cell transplantation is the only curative option. In these patients, we aimed to compare the results of a myeloablative transplant versus a sequential approach consisting in a cytoreductive chemotherapy followed by a reduced intensity conditioning regimen and prophylactic donor lymphocytes infusions. We retrospectively analyzed 99 patients aged 18‐50 years, transplanted for a refractory (52%) or a relapsed AML not in remission (48%). Fifty‐eight patients received a sequential approach and 41 patients a myeloablative conditioning regimen. Only 6 patients received prophylactic donor lymphocytes infusions. With a median follow‐up of 48 months, 2‐year overall survival was 39%, 95% confidence interval (CI) (24‐53) in the myeloablative group versus 33%, 95% CI (21‐45) in the sequential groups (P = .39), and 2‐year cumulative incidence of relapse (CIR) was 57% versus 50% respectively (P = .99). Nonrelapse mortality was not higher in the myeloablative group (17% versus 15%, P = .44). In multivariate analysis, overall survival, CIR and nonrelapse mortality remained similar between the two groups. However, in multivariate analysis, sequential conditioning led to fewer acute grade II‐IV graft versus host disease (GVHD) (HR for sequential approach = 0.37; 95% CI: 0.21‐0.65; P < .001) without a significant impact on chronic GVHD (all grades and extensive). In young patients with refractory or relapsed AML, myeloablative transplant and sequential approach offer similar outcomes except for a lower incidence of acute GvHD after a sequential transplant.
DHEAS patterning across childhood in three sub‐Saharan populations: Associations with age, sex, ethnicity, and cortisol
Authors: Helfrecht Courtney , Hagen Edward H. , DeAvila David , Bernstein Robin M. , Dira Samuel J. , Meehan Courtney L.
Published: December 2017

Objectives

Hormones have many roles in human ontogeny, including the timing of life history ‘switch points’ across development. Limited hormonal data exist from non‐Western children, leaving a significant gap in our understanding of the diversity of life history patterning. This cross‐sectional study examines dehydroepiandrosterone sulfate (DHEAS) production in relation to age, sex, ethnicity, and cortisol concentrations, as well as average age of adrenarche, among Aka and Ngandu children of the Central African Republic and Sidama children of Ethiopia.

Methods

Hair was collected from 480 children (160 per population) aged 3‐18 years old. These samples were analyzed for DHEAS and cortisol concentrations using ELISAs. A generalized additive model was used to examine DHEAS patterning in relation to age, sex, cortisol, and ethnicity. The derivative of DHEAS as a function of age was used to identify average age of adrenarche in each population.

Results

DHEAS patterning in these three populations is distinct from Euro‐American patterns of production. In all three groups, the population‐level age at adrenarche onset occurs slightly later than Euro‐American averages, with both Central African populations experiencing a later onset than the Ethiopian population.

Conclusions

DHEAS patterns and age at adrenarche vary across cultures, perhaps indicating adaptive life history responses in diverse eco‐cultural environments. Delayed involution of the fetal zone and DHEAS patterning may offer both cognitive protection and immune defense in high‐risk, nutritionally‐poor environments. Additional research in the majority world is essential to improving our understanding of the diversity of hormonal development and timing of ‘switch points’ in life history trajectories.
Job insecurity and depression among automobile sales workers: A longitudinal study in South Korea
Authors: Kim Yugyun , Kim Seung‐Sup
Published: December 2017

Background

Job insecurity, the subjective perception of fear due to uncertainty about job continuity, could have long‐term health effects. We aimed to examine the effect of job insecurity on depression among automobile sales workers in South Korea.

Methods

We analyzed data collected in 2007 and 2014 from a longitudinal cohort of 560 sales workers from an automobile company in South Korea. Change in job insecurity was classified into four groups: secure to secure; insecure to secure; secure to insecure; and insecure to insecure.

Results

After adjusting for potential confounders, workers in the insecure to insecure group had a significantly higher likelihood of depression in 2014 than workers in the secure to secure group (OR: 2.74; 95%CI: 1.41, 5.31).

Conclusions

We found that chronic job insecurity may be a risk factor for developing depression among Korean automobile sales workers. This is the first longitudinal study examining the association between job insecurity and depression in South Korea.
A Bioresistant Nitroxide Spin Label for In‐Cell EPR Spectroscopy: In Vitro and In Oocytes Protein Structural Dynamics Studies
Authors: Karthikeyan Ganesan , Bonucci Alessio , Casano Gilles , Gerbaud Guillaume , Abel Sébastien , Thomé Virginie , Kodjabachian Laurent , Magalon Axel , Guigliarelli Bruno , Belle Valérie , Ouari Olivier , Mileo Elisabetta
Published: December 2017

Approaching protein structural dynamics and protein–protein interactions in the cellular environment is a fundamental challenge. Owing to its absolute sensitivity and to its selectivity to paramagnetic species, site‐directed spin labeling (SDSL) combined with electron paramagnetic resonance (EPR) has the potential to evolve into an efficient method to follow conformational changes in proteins directly inside cells. Until now, the use of nitroxide‐based spin labels for in‐cell studies has represented a major hurdle because of their short persistence in the cellular context. The design and synthesis of the first maleimido‐proxyl‐based spin label (M‐TETPO) resistant towards reduction and being efficient to probe protein dynamics by continuous wave and pulsed EPR is presented. In particular, the extended lifetime of M‐TETPO enabled the study of structural features of a chaperone in the absence and presence of its binding partner at endogenous concentration directly inside cells.
Light‐Driven C−H Oxygenation of Methane into Methanol and Formic Acid by Molecular Oxygen Using a Perfluorinated Solvent
Authors: Ohkubo Kei , Hirose Kensaku
Published: December 2017

The chlorine dioxide radical (ClO2.) was found to act as an efficient oxidizing agent in the aerobic oxygenation of methane to methanol and formic acid under photoirradiation. Photochemical oxygenation of methane occurred in a two‐phase system comprising perfluorohexane and water under ambient conditions (298 K, 1 atm). The yields of methanol and formic acid were 14 and 85 %, respectively, with a methane conversion of 99 % without formation of the further oxygenated products such as CO2 and CO. Ethane was also photochemically converted into ethanol (19 %) and acetic acid (80 %). The methane oxygenation is initiated by the photochemical Cl−O bond cleavage of ClO2. to generate Cl. and O2. The produced Cl. reacts with CH4 to form a methyl radical (CH3.). Finally, the oxygenated products such as methanol and formic acid were given by the radical chain reaction. A fluorous solvent plays an important role of inhibiting the deactivation of reactive radical species such as Cl. and CH3..
Copper‐Catalyzed Enantioselective Markovnikov Protoboration of α‐Olefins Enabled by a Buttressed N‐Heterocyclic Carbene Ligand
Authors: Cai Yuan , Yang Xin‐Tuo , Zhang Shuo‐Qing , Li Feng , Li Yu‐Qing , Ruan Lin‐Xin , Hong Xin , Shi Shi‐Liang
Published: December 2017

Reported is a highly enantioselective copper‐catalyzed Markovnikov protoboration of unactivated terminal alkenes. A variety of simple and abundant feedstock α‐olefins bearing a diverse array of functional groups and heterocyclic substituents can be used as substrates, and the reaction proceeds under mild reaction conditions at ambient temperature to provide expedient access to enantioenriched alkylboronic esters in good regioselectivity and with excellent enantiocontrol. Critical to the success of the protocol was the development and application of a novel, sterically hindered N‐heterocyclic carbene, (R,R,R,R)‐ANIPE, as the ligand for copper.
Dicarboxylic Acid Separation by Dynamic and Size‐Matched Recognition in Solution and in the Solid State
Authors: Kumar Vijith , Pilati Tullio , Terraneo Giancarlo , Ciancaleoni Gianluca , Macchioni Alceo , Resnati Giuseppe , Metrangolo Pierangelo
Published: December 2017

Bis(trimethylammonium) alkane diiodides dynamically encapsulate dicarboxylic acids through intermolecular hydrogen bonds between the I− anions of the hosts and the carboxylic OH groups of the guests. A selective recognition is realized when the size of the I−⋅⋅⋅HOOC(CH2/CF2)nCOOH⋅⋅⋅I− superanion matches the dication alkyl chain length. Dynamic recognition is also demonstrated in solution, where the presence of the size‐matching organic salt boosts the acid solubility profile, thus allowing efficient mixture separation.
Thioketone‐Directed Palladium(II)‐Catalyzed C−H Arylation of Ferrocenes with Aryl Boronic Acids
Authors: Cai Zhong‐Jian , Liu Chen‐Xu , Gu Qing , You Shu‐Li
Published: December 2017

A palladium(II)‐catalyzed thioketone‐chelation‐assisted direct C−H arylation of ferrocenes is described. With thioketone as an efficient directing group, various monoaryl‐ and diaryl‐substituted thiocarbonylferrocenes were obtained by palladium‐catalyzed direct C−H functionalization in high yields under mild and base‐free reaction conditions. Furthermore, the arylated thiocarbonylferrocene could undergo diverse transformations.
Building Organic/Inorganic Hybrid Interphases for Fast Interfacial Transport in Rechargeable Metal Batteries
Authors: Zhao Qing , Tu Zhengyuan , Wei Shuya , Zhang Kaihang , Choudhury Snehashis , Liu Xiaotun , Archer Lynden A.
Published: December 2017

We report a facile in situ synthesis that utilizes readily accessible SiCl4 cross‐linking chemistry to create durable hybrid solid–electrolyte interphases (SEIs) on metal anodes. Such hybrid SEIs composed of Si‐interlinked OOCOR molecules that host LiCl salt exhibit fast charge‐transfer kinetics and as much as five‐times higher exchange current densities, in comparison to their spontaneously formed analogues. Electrochemical analysis and direct optical visualization of Li and Na deposition in symmetric Li/Li and Na/Na cells show that the hybrid SEI provides excellent morphological control at high current densities (3–5 mA cm−2) for Li and even for notoriously unstable Na metal anodes. The fast interfacial transport attributes of the SEI are also found to be beneficial for Li‐S cells and stable electrochemical cycling was achieved in galvanostatic studies at rates as high as 2 C. Our work therefore provides a promising approach towards rational design of multifunctional, elastic SEIs that overcome the most serious limitations of spontaneously formed interphases on high‐capacity metal anodes.
ortho‐Directing Chromium Arene Complexes as Efficient Mediators for Enantiospecific C(sp2)–C(sp3) Cross‐Coupling Reactions
Authors: Bigler Raphael , Aggarwal Varinder K.
Published: December 2017

A new strategy for the coupling of a broad scope of electronically diverse aromatics to boronic esters is reported. The coupling sequence, which relies on the directed ortho‐lithiation of chromium arene complexes followed by boronate formation and oxidation, occurs with complete ortho‐selectivity and enantiospecificity to give the coupling products in excellent yields and with high functional group tolerance. An intermediate chromium arene boronate complex was characterized by X‐ray, NMR, and IR experiments to elucidate the reaction mechanism.
Mixed phase Fe2O3/Mn3O4 magnetic nanocomposite for enhanced adsorption of methyl orange dye: Neural network modeling and response surface methodology optimization
Authors: Bhowmik Mahashweta , Deb Krishna , Debnath Animesh , Saha Biswajit
Published: December 2017

In this research, a novel magnetic mesoporous adsorbent with mixed phase of Fe2O3/Mn3O4 nanocomposite was prepared by a facile precipitating method and characterized extensively. The prepared nanocomposite was used as adsorbent for toxic methyl orange (MO) dye removal from aqua matrix considering its high surface area (178.27 m2/g) with high saturation magnetization (23.07 emu/g). Maximum dye adsorption occurs at solution pH 2.0 and the electrostatic attraction between anionic form of MO dye molecules and the positively charged nanocomposite surface is the main driving force behind this adsorption. Response surface methodology (RSM) was used for optimizing the process variables and maximum MO removal of 97.67% is obtained at optimum experimental condition with contact time, adsorbent dose and initial MO dye concentration of 45 min, 0.87 g/l and 116 mg/l, respectively. Artificial neural network (ANN) model with optimum topology of 3–5–1 was developed for predicting the MO removal (%), which has shown higher predictive ability than RSM model. Maximum adsorption capacity of this nanocomposite was found to be 322.58 mg/g from Langmuir isotherm model. Kinetic studies reveal the applicability of second‐order kinetic model with contribution of intra‐particle diffusion in this process.
Solid‐phase organic synthesis of chiral, non‐racemic 1,2,4‐trisubstituted 1,4‐diazepanes with high σ1 receptor affinity
Authors: Fanter Lena , Schepmann Dirk , Wünsch Bernhard
Published: December 2017

The aim of this work was to transfer the established chiral‐pool synthesis of 1,2,4‐trisubstituted 1,4‐diazepanes in solution on the solid phase. For this purpose, (S)‐configured amino acids, (S)‐alanine, and (S)‐leucine, with a small methyl and a larger isobutyl moiety were attached to the solid support 9 by reductive amination. After five reaction steps on the solid support, the 1,4‐diazepanes (S)‐19a,b were cleaved off and reductively alkylated to afford the 1,2,4‐trisubstituted 1,4‐diazepanes (S)‐20a and (S)‐21b, respectively. Both compounds show high σ1 affinity and selectivity over the σ2 subtype.
Block Copolymer Self‐Assembly in Solution—Quo Vadis?
Authors: Brendel Johannes C. , Schacher Felix H.
Published: December 2017

The desire to increase complexity while maintaining control over every aspect of the process itself might be used as a provocative description of the developments in block copolymer self‐assembly in solution over the last decade. The community has witnessed tremendous progress, not only with regard to the design of building blocks, but also in terms of understanding assembly pathways, interfacial properties, or kinetic obstacles. In particular, the latter can be of interest (and actually turned into an advantage) if structures that are not in thermodynamic equilibrium are targeted. Within this focus review, we aim to highlight the key developments and trends that we have identified during the last five years: the development of step‐wise and dynamic processes, different means to impart further hierarchy into solution‐borne nanostructures, and a partial shift in focus towards gradient and bottlebrush block copolymers.
Current state of bioethanol fuel blends in Mexico
Authors: Galicia‐Medina Cynthia M. , Barrios‐Estrada Carlos , Esquivel‐Hernández Diego A. , de Jesús Rostro‐Alanís Magdalena , Torres J. Antonio , Parra‐Saldívar Roberto
Published: December 2017

Environmental damage concerns combined with low levels of domestic gasoline production and high import amounts makes it imperative for Mexico to seek renewable biofuel sources. This paper focuses on bioethanol research at public and private research centers, the regulatory framework and potential of second‐generation bioethanol production, current and failed bioethanol introduction attempts, and a recent plan for a pilot introduction in three states in Mexico. Second‐generation bioethanol based on agroindustry byproducts is a promising alternative. For example, 218 000 m3of bioethanol could be produced annually from agave bagasse solids exceeding the estimated 123 000 m3needed for the pilot program. However, knowledge gaps, an inadequate regulatory status, an unsuitable indifference price, and lack of government support to establish in Mexico a bioethanol industry have delayed its introduction. Finding solutions to factors preventing the introduction of 6% bioethanol to replace gasoline additives would benefit the environment and initiate Mexico's path to lower its dependence on nonrenewable fuels and gasoline imports. © 2017 Society of Chemical Industry and John Wiley & Sons, Ltd
Simultaneous determination of residues of metalaxyl, cyazofamid and a cyazofamid metabolite in tobacco leaves and soil by liquid chromatography with tandem mass spectrometry
Authors: Wu Sizhuo , Yu Weiwei , Sun Caiyuan , Zheng Kunming , Zhang Haizhen , Huang Min , Hu Deyu , Zhang Kankan
Published: December 2017

A simple method was developed and validated for the simultaneous determination of metalaxyl, cyazofamid and the cyazofamid metabolite 4‐chloro‐5‐p‐tolylimidazole‐2‐carbonitrile (CCIM) by liquid chromatography with tandem mass spectrometry. The three target compounds were extracted from tobacco and soil with acetonitrile containing 0.1% acetic acid, and the extracts were purified using octadecylsilane. The proposed method showed satisfactory linearity (R2 ≥ 0.9985) for the target compounds. The limits of detection for metalaxyl, cyazofamid and CCIM were 0.006, 0.06 and 0.06 mg/kg in soil and green tobacco leaves and 0.03, 0.3 and 0.3 mg/kg in cured tobacco leaves, respectively. The limits of quantification for metalaxyl, cyazofamid and CCIM were 0.02, 0.2 and 0.2 mg/kg in soil and green tobacco leaves and 0.1, 1 and 1 mg/kg in cured tobacco leaves, respectively. The average recoveries from soil and tobacco were 72.91–98.40% for metalaxyl, 76.73–105.80% for cyazofamid and 74.48–106.45% for CCIM. The relative standard deviation range was 1.23–6.99%. The developed method was successfully applied to analysis of residues of metalaxyl, cyazofamid and CCIM in real soil and tobacco samples. The results indicated that the established method could meet the requirement for the analysis of trace amounts of all three analytes in soil and tobacco.
Characterization of forsythoside A metabolites in rats by a combination of UHPLC‐LTQ‐Orbitrap mass spectrometer with multiple data processing techniques
Authors: Wang Fei , Cao Guang‐shang , Li Yun , Xu Lu‐lu , Wang Zhi‐bin , Liu Ying , Lu Jian‐qiu , Zhang Jia‐yu
Published: December 2017

Forsythoside A (FTA), the main active constituent isolated from Fructus Forsythiae, has various biological functions including anti‐oxidant, anti‐viral and anti‐microbial activities. However, while research on FTA has been mainly focused on the treatment of diseases on a material basis, FTA metabolites in vivo have not been comprehensively evaluated. Here, a rapid and sensitive method using a UHPLC‐LTQ‐Orbitrap mass spectrometer with multiple data processing techniques including high‐resolution extracted ion chromatograms, multiple mass defect filters and diagnostic product ions was developed for the screening and identification of FTA metabolites in rats. As the result, a total of 43 metabolites were identified in biological samples including 42 metabolites in urine, 22 metabolites in plasma and 15 metabolites in feces. These results demonstrated that FTA underwent a series of in vivo metabolic reactions including methylation, dimethylation, sulfation, glucuronidation, diglucuronidation, cysteine conjugation and their composite reactions. The research enhanced our understanding of FTA metabolism and built a foundation for further toxicity and safety studies.
Pictorial essay of ultrasound‐reconstructed coronal plane images of the uterus in different uterine pathologies
Authors: Grigore Mihaela , Grigore Anamaria , Gafitanu Dumitru , Furnica Cristina
Published: December 2017

Imaging in the major planes (horizontal, coronal, and sagittal) of the uterus is important for determining anatomy and allowing the findings to be standardized, and for evaluating and diagnosing different pathological conditions in clinical practice. Examination of the coronal plane is an important step in identifying uterine pathologies and their relationships to the endometrial canal. Three‐dimensional (3D) ultrasound reveals the normal anatomy better and improves the depiction of abnormal anatomy, as the coronal plane of the uterus can easily be obtained using 3D reconstruction techniques. Our pictorial essay demonstrates that adding 3D ultrasound to a routine gynecological workup can be beneficial for clinicians, enabling a precise diagnosis to be made. In addition, the volumes obtained and stored by 3D ultrasound can allow students or residents to become more familiar with normal and abnormal pelvic structures. Clin. Anat. 31:373–379, 2018. © 2017 Wiley Periodicals, Inc.
Morphological variations of the human ejaculatory ducts in relation to the prostatic urethra
Authors: Malalasekera Ajith Peiris , Sivasuganthan K. , Sarangan S. , Thaneshan K. , Weerakoon D. N. , Mathangasinghe Y. , Gunasekera Chathuri Lakshani , Mallawaarachchi Sudaraka , Nanayakkara Nuwan Dayananda , Anthony D. J. , Ediriweera D.
Published: December 2017

Loss of ejaculation can follow transurethral resection of the prostate (TURP). Periverumontanal prostate tissue is preserved in ejaculation‐preserving TURP (ep‐TURP). Knowledge of ejaculatory duct anatomy in relation to the prostatic urethra can help in ep‐TURP. This was evaluated in cross‐sections of the prostate using a 3 D model to determine a safe zone for resecting the prostate in ep‐TURP. A 3 D reconstruction of the ejaculatory ducts was developed on the basis of six prostate gland cross‐sections. The measurements obtained from the 3 D model were standardized according to the maximum width of the prostate. Simple linear regressions were used to predict the relationships of the ejaculatory ducts. The maximum widths of the prostates ranged from 22.60 to 52.10 mm. The ejaculatory ducts entered the prostate with a concavity directed posterolaterally. They then proceeded toward the seminal colliculus in a fairly straight course, and from that point they angulated anteromedially. As they opened into the prostatic urethra they diverged. Significant regression models predicted the relationships of the ejaculatory ducts to the prostatic urethra based on the sizes of the prostates. The 3 D anatomy of ejaculatory ducts can be predicted on the basis of prostate width. The ejaculatory ducts can be preserved with 95% accuracy if a block of tissue 7.5 mm from the midline on either side of the seminal colliculus is preserved, up to 10 mm proximal to the level of the seminal colliculus, during TURP. Clin. Anat. 31:456–461, 2018. © 2017 Wiley Periodicals, Inc.
Using App Inventor for creating apps to support m‐learning experiences: A case study
Authors: Ortega García Antonio , Ruiz‐Martínez Antonio , Valencia‐García Rafael
Published: December 2017

Working with specific m‐learning apps is useful for learning/teaching purposes. However, its development requires advanced knowledge in programming mobile devices. We present a case study that evaluates the usefulness of App Inventor as a visual, blocks platform that allows teachers, without any advanced programming knowledge, to develop customized m‐learning apps.
The Anthelmintic Drug Niclosamide and Its Analogues Activate the Parkinson's Disease Associated Protein Kinase PINK1
Authors: Barini Erica , Miccoli Ageo , Tinarelli Federico , Mulholland Katie , Kadri Hachemi , Khanim Farhat , Stojanovski Laste , Read Kevin D. , Burness Kerry , Blow Julian J. , Mehellou Youcef , Muqit Miratul M. K.
Published: December 2017

Mutations in PINK1, which impair its catalytic kinase activity, are causal for autosomal recessive early‐onset Parkinson's disease (PD). Various studies have indicated that the activation of PINK1 could be a useful strategy in treating neurodegenerative diseases, such as PD. Herein, it is shown that the anthelmintic drug niclosamide and its analogues are capable of activating PINK1 in cells through the reversible impairment of the mitochondrial membrane potential. With these compounds, for the first time, it is demonstrated that the PINK1 pathway is active and detectable in primary neurons. These findings suggest that niclosamide and its analogues are robust compounds for the study of the PINK1 pathway and may hold promise as a therapeutic strategy in PD and related disorders.