bluuebunny/crossref_metadata_2025 huggingface dataset:
Evaluation of the Arctic surface radiation budget in CMIP5 models
Authors: Boeke Robyn C. , Taylor Patrick C.
Published: July 2016

The Arctic region is warming at a rate more than double the global average, a trend predicted to continue by all Coupled Model Intercomparison Project 5 (CMIP5) climate models. Despite this consistency, significant intermodel spread exists in the simulated Arctic climate related to differences in the Arctic surface radiation budget. Building upon previous work to characterize and understand surface radiation budget biases in climate models, the annual mean and seasonal cycle of the Arctic surface radiation budget in 17 CMIP5 models using the Historical‐forcing scenario is evaluated against state‐of‐the‐art Cloud and Earth's Radiant Energy System Surface Energy Balanced and Filled data. The CMIP5 multimodel ensemble is found to simulate longwave surface fluxes well during the sunlit months (~1 W m−2 differences in July) but exhibits significant wintertime biases (up to −19 W m−2). Shortwave fluxes show substantial across‐model spread during summer; the model standard deviation approaches 20 W m−2 in July. Applying a decomposition analysis to the cloud radiative effect (CRE) seasonal cycles, an unrealistic compensation is uncovered between the model‐simulated seasonal cycles of cloud fraction, all‐sky/clear‐sky flux differences, and surface albedo that enables models to simulate realistic CRE seasonal cycles with unrealistic individual contributions. This unrealistic behavior in models must be constrained to improve Arctic climate simulation; observational uncertainty is sufficient to do so. Lastly, biases in all and clear‐sky longwave downwelling fluxes positively correlate with model surface temperature in winter, while in summer surface temperature is most strongly related to clear‐sky upwelling radiation biases from surface albedo errors.
Author contributions can be clarified
Authors: Ghan Steven , Crawford James , Langematz Ulrike , Leung Ruby , Li Zhanqing , Russell Lynn , Steiner Allison , Zhang Chidong
Published: July 2016

Key Points

Author order is an ambiguous indicator of contribution

Greater clarity is needed

The optional CrediT standard provides greater clarity
A copula‐based nonstationary frequency analysis for the 2012–2015 drought in California
Authors: Kwon Hyun‐Han , Lall Upmanu
Published: July 2016

Using a multicentury reconstruction of drought, we investigate how rare the 2012–2015 California drought is. A Bayesian approach to a nonstationary, bivariate probabilistic model, including the estimation of copula parameters is used to assess the time‐varying return period of the current drought. Both the duration and severity of drought exhibit similar multicentury trends. The period from 800 to 1200 A.D. was perhaps more similar to the recent period than the period from 1200 to 1800 A.D. The median return period of the recent drought accounting for both duration and severity, varies from approximately 667–2652 years, if the model parameters from the different time periods are considered. However, we find that the recent California drought is of unprecedented severity, especially given the relatively modest duration of the drought. The return period of the severity of the recent drought given its 4 year duration is estimated to be nearly 21,000 years.
Thermoelectric Properties of Polymeric Mixed Conductors
Authors: Ail Ujwala , Jafari Mohammad Javad , Wang Hui , Ederth Thomas , Berggren Magnus , Crispin Xavier
Published: July 2016

The thermoelectric (TE) phenomena are intensively explored by the scientific community due to the rather inefficient way energy resources are used with a large fraction of energy wasted in the form of heat. Among various materials, mixed ion‐electron conductors (MIEC) are recently being explored as potential thermoelectrics, primarily due to their low thermal conductivity. The combination of electronic and ionic charge carriers in those inorganic or organic materials leads to complex evolution of the thermovoltage (Voc) with time, temperature, and/or humidity. One of the most promising organic thermoelectric materials, poly(3,4‐ethyelenedioxythiophene)‐polystyrene sulfonate (PEDOT‐PSS), is an MIEC. A previous study reveals that at high humidity, PEDOT‐PSS undergoes an ionic Seebeck effect due to mobile protons. Yet, this phenomenon is not well understood. In this work, the time dependence of the Voc is studied and its behavior from the contribution of both charge carriers (holes and protons) is explained. The presence of a complex reorganization of the charge carriers promoting an internal electrochemical reaction within the polymer film is identified. Interestingly, it is demonstrated that the time dependence behavior of Voc is a way to distinguish between three classes of polymeric materials: electronic conductor, ionic conductor, and mixed ionic–electronic conductor.
Plasmonic‐Radiation‐Enhanced Metal Oxide Nanowire Heterojunctions for Controllable Multilevel Memory
Authors: Lin Luchan , Liu Lei , Musselman Kevin , Zou Guisheng , Duley Walt W. , Zhou Y. Norman
Published: July 2016

Nanowire memristor devices that display multilevel memory effects are of great interest for high‐density storage, however, numerous challenges remain in fabricating high‐quality, stable memory units. A plasmonic‐radiation‐enhanced technique is introduced in this work for scalably forming nanowire multilevel memory units with superior properties. Femtosecond laser irradiation of gold‐titanium dioxide nanowire‐gold structures results in plasmonic‐enhanced optical absorption in the TiO2 locally at the metal‐oxide interface. This produces junctions with superior mechanical and electrical contact, and engineers a concentration of charged defects in the TiO2 near the interface, which enables stable multilevel memory behavior without the need for a traditional electroforming step. The memory units produced display eight‐level current amplification under continuous forward voltage cycles, and can replicate complex multilevel memory sequences without interference between the different multilevel states.
Skin‐Like Oxide Thin‐Film Transistors for Transparent Displays
Authors: Lee Han Eol , Kim Seungjun , Ko Jongbeom , Yeom Hye‐In , Byun Chun‐Won , Lee Seung Hyun , Joe Daniel J. , Im Tae‐Hong , Park Sang‐Hee Ko , Lee Keon Jae
Published: July 2016

Flexible transparent display is a promising candidate to visually communicate with each other in the future Internet of Things era. The flexible oxide thin‐film transistors (TFTs) have attracted attention as a component for transparent display by its high performance and high transparency. The critical issue of flexible oxide TFTs for practical display applications, however, is the realization on transparent and flexible substrate without any damage and characteristic degradation. Here, the ultrathin, flexible, and transparent oxide TFTs for skin‐like displays are demonstrated on an ultrathin flexible substrate using an inorganic‐based laser liftoff process. In this way, skin‐like ultrathin oxide TFTs are conformally attached onto various fabrics and human skin surface without any structural damage. Ultrathin flexible transparent oxide TFTs show high optical transparency of 83% and mobility of 40 cm2 V−1 s−1. The skin‐like oxide TFTs show reliable performance under the electrical/optical stress tests and mechanical bending tests due to advanced device materials and systematic mechanical designs. Moreover, skin‐like oxide logic inverter circuits composed of n‐channel metal oxide semiconductor TFTs on ultrathin, transparent polyethylene terephthalate film have been realized.
Multistability in Bistable Ferroelectric Materials toward Adaptive Applications
Authors: Ghosh Anirban , Koster Gertjan , Rijnders Guus
Published: July 2016

Traditionally thermodynamically bistable ferroic materials are used for nonvolatile operations based on logic gates (e.g., in the form of field effect transistors). But, this inherent bistability in these class of materials limits their applicability for adaptive operations. Emulating biological synapses in real materials necessitates gradual tuning of resistance in a nonvolatile manner. Even though in recent years few observations have been made of adaptive devices using a ferroelectric, the principal question as to how to make a ferroelectric adaptive has remained elusive in the literature. Here, it is shown that by locally controlling the nucleation energy distribution at the ferroelectric–electrode interface multiple‐addressable states in a ferroelectric can be created, which is necessary for adaptive/synaptic applications. This is realized by depositing a layer of nonswitchable ZnO on top of thin film ferroelectric PbZr
x
Ti(1–

x

)O3. This methodology of interface‐engineered ferroelectric should enable realising brain‐like adaptive/synaptic memory in complementary metal‐oxide‐semiconductor (CMOS) devices. Furthermore, the temporally stable multistability in ferroelectrics should enable the designing of multistate memory and logic devices.
Narrow‐Gap Quantum Wires Arising from the Edges of Monolayer MoS2Synthesized on Graphene
Authors: Shi Jianping , Zhou Xiebo , Han Gao‐Feng , Liu Mengxi , Ma Donglin , Sun Jingyu , Li Cong , Ji Qingqing , Zhang Yu , Song Xiuju , Lang Xing‐You , Jiang Qing , Liu Zhongfan , Zhang Yanfeng
Published: July 2016

MoS2/graphene (MoS2/Gr) vertical heterostructures have exhibited great application potentials in high speed electronic and optoelectronic devices, as well as efficient electrocatalysts in hydrogen evolution reaction (HER). The electronic property at the edge of monolayer MoS2is an essential parameter for addressing such applications. Herein, it is reported that, for monolayer MoS2synthesized on Gr/Au foils by chemical vapor deposition, a dramatic decrease of the bandgap from ≈2.20 to ≈0.30 eV occurs at the domain edge within a lateral distance of ≈6 nm, as evidenced by scanning tunneling microscopy/spectroscopy observations. The edges of monolayer MoS2on Gr/Au foils can thus be regarded as narrow‐gap quantum wires considering of their reduced bandgaps. More intriguingly, it is found that this bandgap decrease at the domain edge is closely related to the rather high HER performance for MoS2/Gr/Au foils comparing with that of MoS2/Au foils. Briefly, this work should propel the band structure investigations for MoS2/Gr stacks and their applications in energy related fields.
Synthesis of Radio‐Opaque Methacrylate Monomer and its Application in Visible Light‐Curable Dental Resin
Authors: Zhu Wenbin , Liu Fang , He Jingwei
Published: July 2016

An iodine‐containing mono‐methacrylate 1‐(methacryloxy‐2‐ethoxyamino‐ carbonyl)methyl‐2‐iodine‐benzene (MEMIB) was synthesized as a radiopacified agent and incorporated into Bis‐GMA/TEGDMA resin system with the aim of preparing a radio‐opaque dental resin system. Double bond conversion (DC) was determined by FT‐IR analysis. Volumetric shrinkage (VS) was measured through a variation in density before and after irradiation. Water sorption (WS) and solubility (SL) were obtained until the mass variation of polymer in distilled water was kept stable. Flexural strength (FS) and modulus (FM) were measured using a three‐point bending set up. Bis‐GMA/TEGDMA without MEMIB was used as control. ANOVA analysis revealed that MEMIB could endow dental resin with radiopacity, and radiopacity increased with the increasing of MEMIB concentration. Compared with the control resin, resin with MEMIB also had advantages like higher DC, lower VS, lower WS, and higher FS and FM. All of these implied that MEMIB had the potential to be used as a radiopacified agent and to be applied in dentistry.
Phenylquinoline Derivatives as Efficient Interfacial Layer Materials for High‐Performance Organic Electronic Devices
Authors: Gunasekar Kumarasamy , Cho Woosum , Long Dang Xuan , Reddy Saripally Sudhaker , Song Myungkwan , Noh Yong‐Young , Jin Sung‐Ho
Published: July 2016

Thin film electronic and optoelectronic devices demand electrodes with a work function (Φ) that is sufficiently low to facilitate the transport of electrons in and out of the lowest unoccupied molecular orbital of a given semiconductor. Herein, phenothiazine‐, carbazole‐, and fluorene‐based phenylquinoline derivatives as efficient interfacial layer (IL) materials for solution‐processable organic and metal oxide electronic devices are reported. The IL is applied on top of a charge injection electrode in various solution‐processed devices, including n‐channel organic thin‐film transistors (OTFTs) with [6,6]‐phenyl C71‐butyric acid methyl ester (PC71BM) and poly[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4:5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene) [P(NDI2OD‐T2)] and amorphous indium gallium zinc oxide (IGZO) transistors, and also in organic photovoltaics (OPVs). Both PC71BM‐ and P(NDI2OD‐T2)‐based n‐channel OTFTs with IL show enhanced mobility by more than 200% compared to bare Au electrode. IGZO transistors showed much improved mobility of 15.3 cm2 V−1 s−1 with an IL compared to bare Au (0.6 cm2 V−1 s−1 ) device. A significantly improved power conversion efficiency (PCE) of 7.63% is obtained for IL utilizing the poly[4,8‐bis[(2‐ethylhexyl)oxy]benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl][3‐fluoro‐2‐[(2‐ethylhexyl)carbonyl]thieno[3,4‐b]‐thiophenediyl] (PTB7):PC71BM based OPVs compared to 4.75% of control device. Ultraviolet photoelectron spectroscopy study reveals that phenylquinoline derivatives significantly lower the Φ of Au, thus facilitating electron injection/extraction in the device.
Graphene Transistors Gated by Salted Proton Conductor
Authors: Kim Hyunwoo , Kim Beom Joon , Sun Qijun , Kang Moon Sung , Cho Jeong Ho
Published: July 2016

The first use of proton conductors for gating graphene transistors is demonstrated. The proton conductor used in this study, [poly(styrenesulfonic acid)], is added with sodium halide salts in order to improve the capacitive characteristics of the electrolyte gate dielectric. The influence of the added sodium halide salts (NaF, NaCl, NaBr, and NaI), the salt concentration, and the relative humidity on the dielectric properties of the electrolyte are investigated systematically. Substantial enhancement in the device performances of the graphene transistors including carrier mobility, device ON current, Dirac voltage, and device cut‐off frequency is attained with the addition of the sodium halide salts. From the optimized conditions based on NaI salts, the graphene transistors exhibit hole and electron mobilities of 1900 and 990 cm2 V–1 s–1, respectively, with Dirac voltage near 0 V. Moreover, the cut‐off frequency of the device presenting the dynamic characteristics of a transistor reach up to 100 kHz.
An Inherent Multifunctional Sellotape Substrate for High‐Performance Flexible and Wearable Organic Single‐Crystal Nanowire Array‐Based Transistors
Authors: Shang Qixun , Deng Wei , Zhang Xiujuan , Wang Liang , Huang Liming , Jie Jiansheng
Published: July 2016

Sellotape, as a flexible, sticky, and lightweight substrate, can be integrated in electronic devices to realize unprecedented and low‐cost applications, such as biomedical devices, wearable electronics, smart clothes, and sensory skin for robotic system. However, very few works have successfully demonstrated fabricating devices on sellotape substrates, primarily because traditional microelectronic processing techniques, including photolithography, metallization, and lift‐off, are incompatible with sellotape. Here a novel tape‐stripping method is demonstrated for large‐area fabrication of high‐performance flexible and wearable organic nanowire array‐based field‐effect transistors (ONWFETs) on sellotape substrates. The copper phthalocyanine ONWFETs on the tapes exhibit high average mobility (≈1.02 cm2 V−1 s−1) as well as high bending and wearing stability. Furthermore, 3D ONWFET circuitry consisting of five vertically stacked layers is demonstrated. Device geometries and electronic properties are maintained with high fidelity after sequential stacking processes. This is so far the first study of ONWFETs on flexible tapes and their applications in wearable or 3D integrated devices. It is anticipated that the novel tape stripping method may help overcome upcoming difficulties for organic flexible electronics.
Thin Metal Transparent Conductive Electrodes Formed by Oblique‐Angle Deposition
Authors: Oh Munsik , Kim Min Soo , Kim Hyunsoo
Published: July 2016

Oblique‐angle deposition (OAD) was recently developed for the fabrication of functional thin films with varying porosity and refractive index. In this study, OAD is used to fabricate excellent thin‐metal transparent conductive electrodes (Thin‐TCEs) with an optical transmittance of >93% at wavelengths of 450–550 nm, and sheet resistance of ≈14 Ω sq–1. The process involved the deposition of a thin Ni (5 nm)/Au (5 nm) bilayer with a tilt angle of 45°, and subsequent thermal annealing in ambient O2 to produce a 10 nm‐thick nickel oxide layer with very uniformly distributed Au nanoparticles, afforded by the enhanced interaction between the ambient gas and the metallic film. The application of the Thin‐TCE to III‐nitride light‐emitting diodes (LEDs) produced 15.4% higher output power and 0.05 V lower forward voltage compared to the reference LEDs. These results indicate that the Thin‐TCE is a promising potential replacement for the ITO TCE currently used in III‐nitride LEDs and organic optoelectronic devices, especially considering their fast and cheap fabrication process, availability for mass production, and better electrical and optical properties.
Tuning carbon molecular sieves for natural gas separations: A diamine molecular approach
Authors: Wenz Graham B. , Koros William J.
Published: July 2016

This article introduces a new postsynthetic modification method for tuning the separation properties of carbon molecular sieve (CMS) membranes. Polymeric hollow fibers of 6FDA/BPDA‐DAM were pyrolyzed to 550°C under inert Argon, and were then exposed to a tetrahydrofuran solution containing PPM levels of paraphenylenediamine dopant. The original goal of the treatment was to modify the morphology in a manner to prevent relaxation of the CMS to suppress physical aging, envisioned to be analogous to that in glassy polymer membranes where reduction of “unrelaxed free volume” causes reduced permeance with a mild increase in selectivity. Results of long‐term CO2 and CH4 permeation experiments of doped fibers showed that aging‐resistant membranes did not result. This fact notwithstanding, results revealed this approach provides a valuable new tuning tool for CMS transport properties. Complementary gas sorption experiments performed suggest the amine dopants tune large ultramicropores, thereby increasing size and shape based diffusion selectivity. © 2016 American Institute of Chemical Engineers AIChE J, 63: 751–760, 2017
Hydrophobic mesoporous acidic resin for hydroxyalkylation/alkylation of 2‐methylfuran and ketone to high‐density biofuel
Authors: Zhang Xiangwen , Deng Qiang , Han Peijuan , Xu Jisheng , Pan Lun , Wang Li , Zou Ji‐Jun
Published: July 2016

Hydroxyalkylation/alkylation of biomass‐derived 2‐methylfuran with cyclic ketones (cyclopentanone and cyclohexanone) has great potential in synthesizing high‐density biofuel. But the conversion and selectivity are still unsatisfactory because the in‐situ formed water decreases the acidity of catalyst and induces side reaction. Herein, hydrophobic mesoporous resins with sulfonic acid group (PS) and fluoride sulfonic acid group (PCS) were synthesized by a simple solvothermal reaction and ion exchange treatment, which have good mesoporous structure with surface area of 300–700 m2/g. Notably, PS and PCS have better hydrophobicity and oleophilicity as compared to widely used sulfonic acid functional amberlyst‐15 and fluoride sulfonic acid functional nafion‐212. In the hydroxyalkylation/alkylation reaction, PS shows higher activity and selectivity than amberlyst‐15 while PCS surpasses nafion‐212. Furthermore, both PS and PCS have good recycling stability in consecutive 5 runs. After hydrodeoxygenation, two high‐density biofuels with density of 0.819 and 0.825 g/mL were obtained. © 2016 American Institute of Chemical Engineers AIChE J, 63: 680–688, 2017
A novel 5q11.2 microdeletion in a child with mild developmental delay and dysmorphic features
Authors: Fontana Paolo , Tortora Cristina , Petillo Roberta , Falco Mariateresa , Miniero Martina , De Brasi Davide , Pisanti Maria Antonietta
Published: July 2016

5q11.2 Deletion is a very rare genomic disorder, and its clinical phenotype has not yet been characterized. This report describes a patient with an 8.6 Mb deletion, showing hypotonia, mild developmental delay, short stature, and distinctive dysmorphic features (frontal bossing, square face, deep‐set eyes, prominent columella, long philtrum, thin lips). © 2016 Wiley Periodicals, Inc.
High resting metabolic rate among Amazonian forager‐horticulturalists experiencing high pathogen burden
Authors: Gurven Michael D. , Trumble Benjamin C. , Stieglitz Jonathan , Yetish Gandhi , Cummings Daniel , Blackwell Aaron D. , Beheim Bret , Kaplan Hillard S. , Pontzer Herman
Published: July 2016

Objectives

Resting metabolic rate (RMR) reflects energetic costs of homeostasis and accounts for 60 to 75% of total energy expenditure (TEE). Lean mass and physical activity account for much RMR variability, but the impact of prolonged immune activation from infection on human RMR is unclear in naturalistic settings. We evaluate the effects of infection on mass‐corrected RMR among Bolivian forager‐horticulturalists, and assess whether RMR declines more slowly with age than in hygienic sedentary populations, as might be expected if older adults experience high pathogen burden.

Materials and Methods

RMR was measured by indirect calorimetry (Fitmate MED, Cosmed) in 1,300 adults aged 20 to 90 and TEE was measured using doubly labeled water (n = 40). Immune biomarkers, clinical diagnoses, and anthropometrics were collected by the Tsimane Health and Life History Project.

Results

Tsimane have higher RMR and TEE than people in sedentary industrialized populations. Tsimane RMR is 18 to 47% (women) and 22 to 40% (men) higher than expected using six standard prediction equations. Tsimane mass‐corrected TEE is similarly elevated compared to Westerners. Elevated leukocytes and helminths are associated with excess RMR in multivariate regressions, and jointly result in a predicted excess RMR of 10 to 15%. After age 40, RMR declines by 69 kcal/decade (p < .0001). Controlling for lean mass and height accounts for 71% of age‐related RMR decline, and adding indicators of infection minimally affects the age slope. The residual level of age‐related decline from age 40 is 1.2% per decade.

Conclusion

High pathogen burden may lead to higher metabolic costs, which may be offset by smaller body mass or other energy‐sparing mechanisms.
Resolving Non‐Specific and Specific Adhesive Interactions of Catechols at Solid/Liquid Interfaces at the Molecular Scale
Authors: Utzig Thomas , Stock Philipp , Valtiner Markus
Published: July 2016

The adhesive system of mussels evolved into a powerful and adaptive system with affinity to a wide range of surfaces. It is widely known that thereby 3,4‐dihydroxyphenylalanine (Dopa) plays a central role. However underlying binding energies remain unknown at the single molecular scale. Here, we use single‐molecule force spectroscopy to estimate binding energies of single catechols with a large range of opposing chemical functionalities. Our data demonstrate significant interactions of Dopa with all functionalities, yet most interactions fall within the medium–strong range of 10–20 kBT. Only bidentate binding to TiO2 surfaces exhibits a higher binding energy of 29 kBT. Our data also demonstrate at the single‐molecule level that oxidized Dopa and amines exhibit interaction energies in the range of covalent bonds, confirming the important role of Dopa for cross‐linking in the bulk mussel adhesive. We anticipate that our approach and data will further advance the understanding of biologic and technologic adhesives.
Hot Electrons at Solid–Liquid Interfaces: A Large Chemoelectric Effect during the Catalytic Decomposition of Hydrogen Peroxide
Authors: Nedrygailov Ievgen I. , Lee Changhwan , Moon Song Yi , Lee Hyosun , Park Jeong Young
Published: July 2016

The study of energy and charge transfer during chemical reactions on metals is of great importance for understanding the phenomena involved in heterogeneous catalysis. Despite extensive studies, very little is known about the nature of hot electrons generated at solid–liquid interfaces. Herein, we report remarkable results showing the detection of hot electrons as a chemicurrent generated at the solid–liquid interface during decomposition of hydrogen peroxide (H2O2) catalyzed on Schottky nanodiodes. The chemicurrent reflects the activity of the catalytic reaction and the state of the catalyst in real time. We show that the chemicurrent yield can reach values up to 10−1 electrons/O2 molecule, which is notably higher than that for solid–gas reactions on similar nanodiodes.
Enantioselective Allylic C−H Oxidation of Terminal Olefins to Isochromans by Palladium(II)/Chiral Sulfoxide Catalysis
Authors: Ammann Stephen E. , Liu Wei , White M. Christina
Published: July 2016

The enantioselective synthesis of isochroman motifs has been accomplished by palladium(II)‐catalyzed allylic C−H oxidation from terminal olefin precursors. Critical to the success of this goal was the development and utilization of a novel chiral aryl sulfoxide‐oxazoline (ArSOX) ligand. The allylic C−H oxidation reaction proceeds with the broadest scope and highest levels of asymmetric induction reported to date (avg. 92 % ee, 13 examples with greater than 90 % ee).
Formamide als Lewis‐Basen‐Katalysatoren in SN‐Reaktionen: Effiziente Transformationen von Alkoholen zu Chloriden, Aminen und Ethern
Authors: Huy Peter H. , Motsch Sebastian , Kappler Sarah M.
Published: July 2016

Ein einfacher Formamidkatalysator ermöglicht effiziente Transformationen von Alkoholen zu Alkylchloriden mit Benzoylchlorid als einzigem Reagenz. Diese nukleophilen Substitutionsreaktionen verlaufen über iminiumaktivierte Alkohole als Intermediate. Die neue Methode, die sogar lösungsmittelfrei durchgeführt werden kann, zeichnet sich durch eine exzellente Kompatibilität mit funktionellen Gruppen, Skalierbarkeit (>100 g) und Abfallbilanz aus (E‐Faktor bis zu 2). Chirale Substrate werden unter einem hohen Grad an stereochemischer Inversion in die entsprechenden Chloride überführt (99 %→≥95 % ee). In einem praktischen Eintopfverfahren konnten die primär gebildeten Chloride direkt zu Aminen, Aziden, Ethern, Sulfiden und Nitrilen weiter umgesetzt werden. Der praktische Nutzen der Methode wurde darüber hinaus in kurzen Synthesen von rac‐Clopidogrel und S‐Fendilin bewiesen.
Emerging Targets in Photopharmacology
Authors: Lerch Michael M. , Hansen Mickel J. , van Dam Gooitzen M. , Szymanski Wiktor , Feringa Ben L.
Published: July 2016

The field of photopharmacology uses molecular photoswitches to establish control over the action of bioactive molecules. It aims to reduce systemic drug toxicity and the emergence of resistance, while achieving unprecedented precision in treatment. By using small molecules, photopharmacology provides a viable alternative to optogenetics. We present here a critical overview of the different pharmacological targets in various organs and a survey of organ systems in the human body that can be addressed in a non‐invasive manner. We discuss the prospects for the selective delivery of light to these organs and the specific requirements for light‐activatable drugs. We also aim to illustrate the druggability of medicinal targets with recent findings and emphasize where conceptually new approaches have to be explored to provide photopharmacology with future opportunities to bring “smart” molecular design ultimately to the realm of clinical use.
Quantum chemistry mechanism study on preventing slag‐bonding via modifying the material surface properties
Authors: Li Mingqiang , Zhang Zhongxiao , Wu Xiaojiang , Fan Junjie
Published: July 2016

A huge amount of coal with high content of Na and K in ash was found in Xinjiang Province, China. However, the most serious ash fouling/slagging problems of that kind of coal usually cause the increasing of operating costs and energy consumption in a power plant. In order to clarify the mechanism of the effect on ash deposition behavior on different material surfaces, the experimental study, as well as quantum chemistry calculation, was used in this study. The results show that the nickel‐based material can significantly alleviate the ash deposition of high‐alkali coal. The adsorption energy between Na atom and NiO is much higher than that between Na atom and Fe2O3. The much lower system energy between Na atom and Fe2O3 will cause more stable system of Na‐Fe2O3. However, for nickel‐based material, the electrons of Na‐NiO system are being at a higher energy status, which will cause the system to stay at a relative unstable status. The quantum chemistry calculation results can well explain the phenomena of the experimental result. Furthermore, the interaction mechanisms between Na and Al‐based materials were also calculated to predict the effect of Al‐based material on preventing ash fouling and slagging. Copyright © 2016 Curtin University of Technology and John Wiley & Sons, Ltd.
Effects of elevated temperature and crude oil on the properties of a hydrogenated nitrile butadiene rubber elastomer
Authors: Pan Long , Tan Jinzhu , Han Xuemei , Li Peng , Zhang Wujian
Published: July 2016

The stability and durability of hydrogenated nitrile butadiene rubber (HNBR) material in crude oil environments are of great importance for petroleum equipment to resist leakage and to ensure reliability. In this paper, an HNBR material was fabricated, and the degradation of the HNBR material was investigated in simulated crude oil environments. One crude oil and three temperatures (50 °C, 75 °C, and 100 °C, based on actual crude oil operations, were used in this study. Weight changes for the HNBR specimens were monitored after exposure to the environments over time. Optical microscopy was used to show the topographical changes on the specimen surfaces. Attenuated total reflection Fourier transform infrared (ATR‐FTIR) spectroscopy was employed to study the surface chemistry of the HNBR material before and after exposure to the simulated crude oil environments at selected times. Mechanical property tests (tensile and compressive stress–strain tests, tear strength test, and compression set test) were conducted to assess the changes in mechanical properties of the HNBR specimens before and after exposure to the environments. The test results show that the physical–mechanical properties of the HNBR material changed significantly. The temperature and the crude oil had a direct effect on the degradation of the mechanical properties. The ATR‐FTIR test results indicate that the surface chemistry changed via chain crosslinking in the material after exposure to the environments over time. The degradation mechanisms of the HNBR material after exposure to the crude oil could be due to the presence of chain crosslinking, chain mobility, and backbone scission. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44012.
Fabrication and characterization of hybrid films based on polyaniline and graphitic carbon nitride nanosheet
Authors: Dinari Mohammad , Momeni Mohamad Mohsen , Afshari Mohaddeseh
Published: July 2016

Hybrid films of polyaniline/graphitic carbon nitride (PANI/g‐C3N4) deposited on titanium was fabricated. First, g‐C3N4 as a two‐dimensional graphite‐like structure was synthesized by the stepwise condensation reaction of melamine and cyanuric chloride in the presence of N,N‐dimethylmethanamide as a high boiling point nonnucleophilic base. Then composite films of PANI/g‐C3N4 were prepared by in situ electrochemical polymerization of an aniline solution containing g‐C3N4. Different concentrations of g‐C3N4 were utilized to improve the electrochemical performances of the hybrids. The resulting PANI/g‐C3N4 composite films were characterized by X‐ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, and ultraviolet–visible diffuse reflection spectroscopy techniques. The electrochemical performance of the composites was evaluated by cyclic voltammetry (CV). Application of the prepared samples has been evaluated as supercapacitor material in 0.5 M H2SO4 solution using CV technique. The specific capacitances of PANI/g‐C3N4 composite films were higher than obtained for pure PANI films. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44059.
A model‐based demand‐balancing control for dynamically divided multiple urban subnetworks
Authors: Lin Shu , Kong Qing‐Jie , Huang Qingming
Published: July 2016

Traffic control is an effective and efficient method for the problem of traffic congestion. It is necessary to design a high‐level controller to regulate the network traffic demands, because traffic congestion is not only caused by the improper management of the traffic network but also to a great extent caused by excessive network traffic demands. Therefore, we design a demand‐balance model predictive controller based on the macroscopic fundamental diagram‐based multi‐subnetwork model, which can optimize the network traffic mobility and the network traffic throughput by regulating the input traffic flows of the subnetworks. Because the transferring traffic flows among subnetworks are indirectly controlled and coordinated by the demand‐balance model predictive controller, the subnetwork division can variate dynamically according to real traffic states, and a global optimality can be achieved for the entire traffic network. The simulation results show the effectiveness of the proposed controller in improving the network traffic throughput. Copyright © 2016 John Wiley & Sons, Ltd.
FK506 binding protein 51 integrates pathways of adaptation
Authors: Rein Theo
Published: July 2016

This review portraits FK506 binding protein (FKBP) 51 as “reactivity protein” and collates recent publications to develop the concept of FKBP51 as contributor to different levels of adaptation. Adaptation is a fundamental process that enables unicellular and multicellular organisms to adjust their molecular circuits and structural conditions in reaction to environmental changes threatening their homeostasis. FKBP51 is known as chaperone and co‐chaperone of heat shock protein (HSP) 90, thus involved in processes ensuring correct protein folding in response to proteotoxic stress. In mammals, FKBP51 both shapes the stress response and is calibrated by the stress levels through an ultrashort molecular feedback loop. More recently, it has been linked to several intracellular pathways related to the reactivity to drug exposure and stress. Through its role in autophagy and DNA methylation in particular it influences adaptive pathways, possibly also in a transgenerational fashion.

Also see the video abstract here.
USP7/HAUSP: A SUMO deubiquitinase at the heart of DNA replication
Authors: Smits Veronique A.J. , Freire Raimundo
Published: July 2016

DNA replication is both highly conserved and controlled. Problematic DNA replication can lead to genomic instability and therefore carcinogenesis. Numerous mechanisms work together to achieve this tight control and increasing evidence suggests that post‐translational modifications (phosphorylation, ubiquitination, SUMOylation) of DNA replication proteins play a pivotal role in this process. Here we discuss such modifications in the light of a recent article that describes a novel role for the deubiquitinase (DUB) USP7/HAUSP in the control of DNA replication. USP7 achieves this function by an unusual and novel mechanism, namely deubiquitination of SUMOylated proteins at the replication fork, making USP7 also a SUMO DUB (SDUB). This work extends previous observations of increased levels of SUMO and low levels of ubiquitin at the on‐going replication fork. Here, we discuss this novel study, its contribution to the DNA replication and genomic stability field and what questions arise from this work.
Detection of spatial change points in the mean and covariances of multivariate simultaneous autoregressive models
Authors: Otto Philipp , Schmid Wolfgang
Published: July 2016

In this paper, we propose a test procedure to detect change points of multidimensional autoregressive processes. The considered process differs from typical applied spatial autoregressive processes in that it is assumed to evolve from a predefined center into every dimension. Additionally, structural breaks in the process can occur at a certain distance from the predefined center. The main aim of this paper is to detect such spatial changes. In particular, we focus on shifts in the mean and the autoregressive parameter. The proposed test procedure is based on the likelihood‐ratio approach. Eventually, the goodness‐of‐fit values of the estimators are compared for different shifts. Moreover, the empirical distribution of the test statistic of the likelihood‐ratio test is obtained via Monte Carlo simulations. We show that the generalized Gumbel distribution seems to be a suitable limiting distribution of the proposed test statistic. Finally, we discuss the detection of lung cancer in computed tomography scans and illustrate the proposed test procedure.
Early‐life single‐episode sevoflurane exposure impairs social behavior and cognition later in life
Authors: Lin Daisy , Liu Jinyang , Kramberg Lea , Ruggiero Andrea , Cottrell James , Kass Ira S.
Published: July 2016

Background

Single‐episode anesthetic exposure is the most prevalent surgery‐related incidence among young children in the United States. Although numerous studies have used animals to model the effects of neonatal anesthetics on behavioral changes later on in life, our understanding of the functional consequences to the developing brain in a comprehensive and clinically relevant manner is unclear.

Methods

The volatile anesthetic, sevoflurane (sevo) was administered to C57BL6 postnatal day 7 (P7) mice in a 40% oxygen and 60% nitrogen gas mixture. In order to examine the effects of sevo alone on the developing brain in a clinically relevant manner, mice were exposed to an average of 2.38 ± 0.11% sevo for 2 h. No sevo (control) mice were treated in an identical manner without sevo exposure. Mice were examined for cognition and neuropsychiatric‐like behavioral changes at 1–5 months of age.

Results

Using the active place avoidance (APA) test and the novel object recognition (NOR) test, we demonstrated that P7 sevo‐treated mice showed a deficit in learning and memory both during periadolescence and adulthood. We then employed a battery of neuropsychiatric‐like behavioral tests to examine social interaction, communication, and repetitive behavior. Interestingly, compared to the no‐sevo–treated group, sevo‐treated mice showed significant reductions in the time interacting with a novel mouse (push–crawl and following), time and interaction in a chamber with a novel mouse, and time sniffing a novel social odor.

Conclusions

Our study established that single‐episode, 2‐h sevo treatment during early life impairs cognition later on in life. With this approach, we also observed neuropsychiatric‐like behavior changes such as social interaction deficits in the sevo‐treated mice. This study elucidated the effects of a clinically relevant single‐episode sevo application, given during the neonatal period, on neurodevelopmental behavioral changes later on in life.
High‐throughput screening of clinically approved drugs that prime polyethylenimine transfection reveals modulation of mitochondria dysfunction response improves gene transfer efficiencies
Authors: Nguyen Albert , Beyersdorf Jared , Riethoven Jean‐Jack , Pannier Angela K.
Published: July 2016

Nonviral gene delivery methods are advantageous over viral vectors in terms of safety, cost, and flexibility in design and application, but suffer from lower gene transfer efficiency. In addition to modifications to nucleic acid design and nonviral carriers, new tools are sought to enhance transfection. Priming is the pharmacological modulation of transfection efficiency and transgene expression, and has demonstrated transfection increase in several compounds, for example, chloroquine and glucocorticoids. To develop a library of transfection priming compounds, a high‐throughput screen was performed of the NIH Clinical Collection (NCC) to identify clinical compounds that prime polyethylenimine (PEI) transfection. HEK293T cells were treated with priming compounds, then transfected with enhanced green fluorescent protein (EGFP)‐encoding plasmid by PEI. After 48‐hr culture, primed and transfected cells were assayed for transfection, cell proliferation, and cell viability by fluorescence measurement of EGFP reporter, Hoechst 33342 nuclei stain, and resazurin metabolic assay. From the microscope image analysis and microplate measurements, transfection fold‐changes were determined, and compounds resulting in statistically significant transfection fold‐change were identified. NCC compounds were clustered using PubChem fingerprint similarity by Tanimoto coefficients in ChemmineTools. Fold‐changes for each compound were linked to drug clusters, from which drug classes that prime transfection were identified. Among the identified drugs classes that primed transfection increases were antioxidants, GABAA receptor modulators, and glucocorticoids. Resveratrol and piceid, stilbenoid antioxidants found in grapes, and zolpidem, a GABAA modulator, increased transfection nearly three‐fold. Literature indicate interaction of the identified transfection priming drug clusters with mitochondria, which may modulate mitochondrial dysfunction known to be associated with PEI transfection.
Reducing neuroinflammation by delivery of IL‐10 encoding lentivirus from multiple‐channel bridges
Authors: Margul Daniel J. , Park Jonghyuck , Boehler Ryan M. , Smith Dominique R. , Johnson Mitchell A. , McCreedy Dylan A. , He Ting , Ataliwala Aishani , Kukushliev Todor V. , Liang Jesse , Sohrabi Alireza , Goodman Ashley G. , Walthers Christopher M. , Shea Lonnie D. , Seidlits Stephanie K.
Published: July 2016

The spinal cord is unable to regenerate after injury largely due to growth‐inhibition by an inflammatory response to the injury that fails to resolve, resulting in secondary damage and cell death. An approach that prevents inhibition by attenuating the inflammatory response and promoting its resolution through the transition of macrophages to anti‐inflammatory phenotypes is essential for the creation of a growth permissive microenvironment. Viral gene delivery to induce the expression of anti‐inflammatory factors provides the potential to provide localized delivery to alter the host inflammatory response. Initially, we investigated the effect of the biomaterial and viral components of the delivery system to influence the extent of cell infiltration and the phenotype of these cells. Bridge implantation reduces antigen‐presenting cell infiltration at day 7, and lentivirus addition to the bridge induces a transient increase in neutrophils in the spinal cord at day 7 and macrophages at day 14. Delivery of a lentivirus encoding IL‐10, an anti‐inflammatory factor that inhibits immune cell activation and polarizes the macrophage population towards anti‐inflammatory phenotypes, reduced neutrophil infiltration at both day 7 and day 28. Though IL‐10 lentivirus did not affect macrophages number, it skewed the macrophage population toward an anti‐inflammatory M2 phenotype and altered macrophage morphology. Additionally, IL‐10 delivery resulted in improved motor function, suggesting reduced secondary damage and increased sparing. Taken together, these results indicate that localized expression of anti‐inflammatory factors, such as IL‐10, can modulate the inflammatory response following spinal cord injury, and may be a key component of a combinatorial approach that targets the multiple barriers to regeneration and functional recovery.
Performance evaluation of learning styles based on fuzzy logic inference system
Authors: Ozdemir Ali , Alaybeyoglu Aysegul , Mulayim Naciye , Balbal Kadriye Filiz
Published: July 2016

Determining best convenient learning style in accordance with the individual's capabilities and personalities is very important for learning rapidly, easily, and in high quality. When it is thought that each individual has different personality and ability, it can be recognized that each individual's best convenient learning style will be different. Because of the importance of lifelong learning, many methods and approaches have been developed to determine learning styles of the individuals. In this study, a rule based fuzzy logic inference system is developed to determine best convenient learning styles of the engineering faculty stuffs and the students. During studies, two different learning style models namely Honey&Mumford and McCarthy are used in implementations. This study is carried out with a total number of 60 and 26 engineering faculty students and stuffs, respectively. The personal information form and Learning Style Preference Survey of Honey&Mumford and McCarthy are used to collect the data which are analyzed using the techniques of frequency, percentage, mean, standard deviation, and t‐test. While Honey&Mumford learning style classifies engineering faculty students and stuffs as Activist, Reflector, Theorist, and Pragmatist; McCarthy learning style classifies them as Innovative, Analytic, Common Sense, and Dynamic. Gender, age, and department are selected as the metrics for evaluation of the system performance. © 2016 Wiley Periodicals, Inc Comput Appl Eng Educ 24:853–865, 2016; View this article online at wileyonlinelibrary.com/journal/cae; DOI 10.1002/cae.21754
Four New Steroidal Glycosides, Protolinckiosides A – D, from the Starfish Protoreaster lincki
Authors: Malyarenko Timofey V. , Kicha Alla A. , Kalinovsky Anatoly I. , Ivanchina Natalia V. , Popov Roman S. , Pislyagin Evgeny A. , Menchinskaya Ekaterina S. , Padmakumar Krishna Pillai , Stonik Valentin A.
Published: July 2016

Four new steroidal glycosides, protolinckiosides A – D (1 – 4, resp.), were isolated along with four previously known glycosides, 5 – 8, from the MeOH/EtOH extract of the starfish Protoreaster lincki. The structures of 1 – 4 were elucidated by extensive NMR and ESI‐MS techniques as (3β,4β,5α,6β,7α,15α,16β,25S)‐4,6,7,8,15,16,26‐heptahydroxycholestan‐3‐yl 2‐O‐methyl‐β‐d‐xylopyranoside (1), (3β,5α,6β,15α,24S)‐3,5,6,8,15‐pentahydroxycholestan‐24‐yl α‐l‐arabinofuranoside (2), sodium (3β,6β,15α,16β,24R)‐29‐(β‐d‐galactofuranosyloxy)‐6,8,16‐trihydroxy‐3‐[(2‐O‐methyl‐β‐d‐xylopyranosyl)oxy]stigmast‐4‐en‐15‐yl sulfate (3), and sodium (3β,6β,15α,16β,22E,24R)‐28‐(β‐d‐galactofuranosyloxy)‐6,8,16‐trihydroxy‐3‐[(2‐O‐methyl‐β‐d‐xylopyranosyl)oxy]ergosta‐4,22‐dien‐15‐yl sulfate (4). The unsubstituted β‐d‐galactofuranose residue at C(28) or C(29) of the side chains was found in starfish steroidal glycosides for the first time. Compounds 1 – 4 significantly decreased the intracellular reactive oxygen species (ROS) content in RAW 264.7 murine macrophages at induction by proinflammatory endotoxic lipopolysaccharide (LPS) from E. coli.
Chemical Constituents of the Rare Cliff Plant Oresitrophe rupifraga and Their Antineuroinflammatory Activity
Authors: Wu Xi‐Ying , Xiong Juan , Liu Xin‐Hua , Hu Jin‐Feng
Published: July 2016

Four new (1 – 4) and thirteen known (5 – 17) compounds were isolated from a rare cliff plant, Oresitrophe rupifraga. Based on spectroscopic evidence, the new structures were established to be [(2S,3R,4R)‐4‐(4‐methoxybenzyl)‐2‐(4‐methoxyphenyl)‐tetrahydrofuran‐3‐yl]methanol (1), (3α)‐23‐(acetyloxy)‐3‐hydroxyolean‐12‐en‐29‐oic acid (2), 3α,23‐(isopropylidenedioxy)olean‐12‐en‐29‐oic acid (3, artifact of isolation), and (3β,15β)‐3‐hydroxycholest‐5‐en‐15‐yl β‐d‐glucopyranoside (4), respectively. Among the isolates, compounds 1, 4, epieudesmin (7), and 1‐O‐(9Z,12Z,15Z‐octadecatrienoyl)glycerol (17) were found to show significant antineuroinflammatory effects by inhibiting the NO production in lipopolysaccharide (LPS)‐stimulated murine BV‐2 microglial cells, with IC50 values of 7.21, 9.39, 4.96, and 8.51 μm, respectively.