bluuebunny/crossref_metadata_2025 huggingface dataset:
Uniform Hollow Mesoporous Nickel Cobalt Sulfide Microdumbbells: A Competitive Electrode with Exceptional Gravimetric/Volumetric Pseudocapacitance for High‐Energy‐Density Hybrid Superapacitors
Authors: Hou Linrui , Bao Ruiqi , Rehan Muhammad , Tong Liuniu , Pang Gang , Zhang Xiaogang , Yuan Changzhou
Published: January 2017

In this contribution, a facile two‐step hydrothermal protocol to prepare hierarchical uniform hollow mesoporous NiCo2S4 microdumbbells (NCS‐MDs) for advanced supercapacitors is developed. Physicochemical investigations reveal that the as‐obtained NCS‐MDs with mesoporous channels in nanoshells possess high‐content Co(III) and Ni(III) species, large surface area (≈80 m2 g−1)/pore volume (≈0.12 m3 g−1), and high tap density (≈0.8 g cm−3). When evaluated as an attractive pseudocapacitive electrode, the unique NCS‐MDs with mass loading of 7 mg cm−2 exhibit remarkable gravimetric/volumetric specific capacitances of ≈912 F g−1 (≈729 F cm−3) at 3 A g−1, and even ≈767 F g−1 (≈613 F cm−3) at high current density of 10 A g−1. Additionally, capacitive degradations of ≈13% and ≈18% are observed over 5000 continous cycles at current rates of 6 and 10 A g−1, respectively. Furthermore, a high‐energy‐density hybrid device is fabricated by using hollow NCS‐MDs and biomass‐derived activated carbon as positive and negative electrodes, respectively, and delivers striking energy density of ≈35.4 Wh kg−1 at power density of ≈381.2 W kg−1, and excellent electrochemical stability at various rates over 11 000 consecutive cycles. These fascinating features strongly highlight that the as‐resulted hollow mesoporous NCS‐MDs could be highly anticipated as a promising electrode platform for next‐generation hybrid supercapacitors.
Synthesis and optimization of membrane cascade for gas separation via mixed‐integer nonlinear programming
Authors: Aliaga‐Vicente Alicia , Caballero José A. , Fernández‐Torres María J.
Published: January 2017

Currently, membrane gas separation systems enjoy widespread acceptance in industry as multistage systems are needed to achieve high recovery and high product purity simultaneously, many such configurations are possible. These designs rely on the process engineer's experience and therefore suboptimal configurations are often the result. This article proposes a systematic methodology for obtaining the optimal multistage membrane flow sheet and corresponding operating conditions. The new approach is applied to cross‐flow membrane modules that separate CO2 from CH4, for which the optimization of the proposed superstructure has been achieved via a mixed‐integer nonlinear programming model, with the gas processing cost as objective function. The novelty of this work resides in the large number of possible interconnections between each membrane module, the energy recovery from the high pressure outlet stream and allowing for nonisothermal conditions. The results presented in this work comprise the optimal flow sheet and operating conditions of two case studies. © 2017 American Institute of Chemical Engineers AIChE J, 63: 1989–2006, 2017
Non‐ionic soft materials influence on filtration resistance and cake dry matter content
Authors: Hinge Mogens , Christensen Morten Lykkegaard
Published: January 2017

Filtration of organic slurries is important in many industries but challenging because the hydraulic resistance is high due to gel materials in the slurries. Particles with solid polystyrene (PS) core and varying amount of poly(N‐isopropylacrylamide) (PNIPAM) gel surface were synthesized. At low amount of gel, the gel deformed and partly filled the cake void increasing the resistance. This was successfully fitted using a semi‐theoretical model for deformable particles. At high amount of gel, the gel deformed filling the entire cake void and the resistance was dominated by the gel. During consolidation, the primary retardation time increased three orders of magnitude with gel thickness as expected as primary consolidation were dominated by the dissipation of pore water. The secondary retardation time also increased but not as pronounced as primary retardation time. Secondary consolidation was due to local compression of the gel and therefore less dependent on gel thickness. © 2017 American Institute of Chemical Engineers AIChE J, 63: 2241–2247, 2017
Lithium n‐Doped Polyaniline as a High‐Performance Electroactive Material for Rechargeable Batteries
Authors: Jiménez Pablo , Levillain Eric , Alévêque Olivier , Guyomard Dominique , Lestriez Bernard , Gaubicher Joël
Published: January 2017

The discovery of conducting lithium‐doped polyaniline with reversible redox chemistry allows simultaneous unprecedented capacity and stability in a non‐aqueous Li battery. This compound (lithium emeraldinate) was synthesized by lithium–proton exchange on the emeraldine base in an anhydrous lithium‐based electrolyte. A combination of UV/Vis‐NIR spectroelectrochemistry, XPS, FTIR, and EQCM characterization allowed a unified description of the chemical and electrochemical behavior, showing facile charge delocalization of the doped states and the reversibility of the redox processes in this form of polyaniline. From a practical point of view, lithium emeraldinate behaves as a high‐capacity organic active material (230 mAh g−1) that enables preparation of relatively thick composite electrodes with a low amount of carbon additives and high energy density (460 Wh kg−1). Concomitantly, at 1C rate, 400 cycles were achieved without significant capacity loss, while the coulombic efficiency is greater than 99 %.
meta‐C−H Bromination on Purine Bases by Heterogeneous Ruthenium Catalysis
Authors: Warratz Svenja , Burns David J. , Zhu Cuiju , Korvorapun Korkit , Rogge Torben , Scholz Julius , Jooss Christian , Gelman Dmitri , Ackermann Lutz
Published: January 2017

Methods for positionally selective remote C−H functionalizations are in high demand. Herein, we disclose the first heterogeneous ruthenium catalyst for meta‐selective C−H functionalizations, which enabled remote halogenations with excellent site selectivity and ample scope. The versatile heterogeneous Ru@SiO2 catalyst was broadly applicable and could be easily recovered and reused, which set the stage for the direct fluorescent labeling of purines. In contrast to palladium, rhodium, iridium, or cobalt complexes, solely the ruthenium catalysis manifold provided access to meta‐halogenated purine derivatives, illustrating the unique power of ruthenium C−H activation catalysis.
Ligand‐Enabled β‐C–H Arylation of α‐Amino Acids Without Installing Exogenous Directing Groups
Authors: Chen Gang , Zhuang Zhe , Li Gen‐Cheng , Saint‐Denis Tyler G. , Hsiao Yi , Joe Candice L. , Yu Jin‐Quan
Published: January 2017

Herein we report acid‐directed β‐C(sp3)‐H arylation of α‐amino acids enabled by pyridine‐type ligands. This reaction does not require the installation of an exogenous directing group, is scalable, and enables the preparation of Fmoc‐protected unnatural amino acids in three steps. The pyridine‐type ligands are crucial for the development of this new C(sp3)‐H arylation.
CO2‐Assisted Fabrication of Two‐Dimensional Amorphous Molybdenum Oxide Nanosheets for Enhanced Plasmon Resonances
Authors: Liu Wei , Xu Qun , Cui Weili , Zhu Chuanhui , Qi Yuhang
Published: January 2017

As a remarkable class of plasmonic materials, two dimensional (2D) semiconductor compounds have attracted attention owing to their controlled manipulation of plasmon resonances in the visible light spectrum, which outperforms conventional noble metals. However, tuning of plasmonic resonances for 2D semiconductors remains challenging. Herein, we design a novel method to obtain amorphous molybdenum oxide (MoO3) nanosheets, in which it combines the oxidation of MoS2 and subsequent supercritical CO2‐treatment, which is a crucial step for the achievement of amorphous structure of MoO3. Upon illumination, hydrogen‐doped MoO3 exhibits tuned surface plasmon resonances in the visible and near‐IR regions. Moreover, a unique behavior of the amorphous MoO3 nanosheets has been found in an optical biosensing system; there is an optimum plasmon resonance after incubation with different BSA concentrations, suggesting a tunable plasmonic device in the near future.
A Double Allylation Strategy for Gram‐Scale Guaianolide Production: Total Synthesis of (+)‐Mikanokryptin
Authors: Hu Xirui , Xu Silong , Maimone Thomas J.
Published: January 2017

With over 5000 members isolated to date, sesquiterpene lactones represent a prolific source of medicinal agents with several derivatives in human clinical trials. The guaianolides, a major subset of this group, have been intensely investigated from both medicinal and chemical‐synthesis perspectives for decades. To date, the myriad stereochemical permutations presented by this enormous family have precluded the synthesis of many unique members. Herein we report the total synthesis of the trans‐fused 8,12‐guaianolide (+)‐mikanokryptin in 10 steps from (+)‐carvone. Notably, this synthesis is the first gram‐scale total synthesis of a guaianolide natural product.
Vertically Aligned Porous Nickel(II) Hydroxide Nanosheets Supported on Carbon Paper with Long‐Term Oxygen Evolution Performance
Authors: Xiong Dehua , Li Wei , Liu Lifeng
Published: January 2017

Vertically aligned Ni(OH)2 nanosheets were grown on carbon paper (CP) current collectors through a simple and cost‐effective hydrothermal approach. The as‐grown nanosheets are porous and highly crystallized. If used as a monolithic electrode for electrochemical water oxidation in alkaline solution, the carbon paper supported Ni(OH)2 nanosheets [CP@Ni(OH)2] exhibit high electrocatalytic activity and excellent long‐term stability. The electrode can attain an anodic current density of 20 mA cm−2 at a low overpotential of 338 mV, comparable to that of state‐of‐the‐art RuO2 nanocatalysts supported on CP (CP/RuO2) with the same catalyst loading. Significantly, CP@Ni(OH)2 shows much better long‐term stability than CP/RuO2 upon continuous galvanostatic electrolysis, particularly at a high industry‐relevant current density such as 100 mA cm−2. CP@Ni(OH)2 can sustain water oxidation at 100 mA cm−2 for 50 h without any degradation, whereas the performance of CP/RuO2 is much poorer and deteriorates gradually over time. CP@Ni(OH)2 electrodes hold substantial promise for use as low‐costing water oxidation anodes in electrolyzers.
Synthesis of β‐Keto Sulfones by a Catalyst‐Free Reaction of Aryldiazonium Tetrafluoroborates, Sulfur Dioxide, and Silyl Enol Ethers
Authors: Liu Tianshuo , Zheng Danqing , Ding Yechun , Fan Xiaona , Wu Jie
Published: January 2017

A green approach for the generation of β‐keto sulfones through a reaction of aryldiazonium tetrafluoroborates and sulfur dioxide with silyl enol ether under catalyst‐ and additive‐free conditions has been realized. This reaction proceeds efficiently at room temperature and goes to completion in half an hour. During the reaction process, aryldiazonium tetrafluoroborate is treated with DABCO⋅(SO2)2 (DABCO=1,4‐diazabicyclo[2.2.2]octane) to provide a sulfonyl radical as the key intermediate, which then initiates the transformation. Oxidants or metal catalysts are avoided, and the presence of DABCO also plays an important role in the reaction.
Ion‐Pair Halogen Bonds in 2‐Halo‐Functionalized Imidazolium Chloride Receptors: Substituent and Solvent Effects
Authors: Nunes Rafael , Costa Paulo J.
Published: January 2017

The interaction of 2‐halo‐functionalized imidazolium derivatives (n‐X+; X=Cl, Br, I) with a chloride anion through ion‐pair halogen bonds (n‐X⋅Cl) was studied by means of DFT and ab initio calculations. A method benchmark was performed on 2‐bromo‐1H‐imidazol‐3‐ium in association with chloride (1‐Br⋅Cl); MP2 yielded the best results when compared with CCSD(T) calculations. The interaction energies (ΔE) in the gas phase are high and, although the electrostatic interaction is strong owing to the ion‐pair nature of the system, large X⋅⋅⋅Cl− Wiberg bond orders and contributions from charge transfer (n
→σ*C−X) are obtained. These values drop considerably in chloroform and water; this shows that solvent plays a role in modulating the interaction and that gas‐phase calculations are particularly unrealistic for experimental applications. The introduction of electron‐withdrawing groups in the 4,5‐positions of the imidazolium (e.g., −NO2, −F) increases the halogen‐bond strength in both the gas phase and solvent, including water. The effect of the substituents on the 1,3‐positions (N−H groups) also depends on the solvent. The variation of ΔE can be predicted through a two‐parameter linear regression that optimizes the weights of charge‐transfer and electrostatic interactions, which are different in vacuum and in solvent (chloroform and water). These results could be used in the rational design of efficient chloride receptors based on halogen bonds that work in solution, in particular, in an aqueous environment.
A Convenient One‐Pot Route to Screw‐Shaped [5]Azahelicenes via Rhodium(III)‐Catalyzed Multiple C−H Bond Activation
Authors: Li Shuai‐Shuai , Liu Chen‐Fei , Zhang Guo‐Tai , Xia Ying‐Qi , Li Wei‐Huan , Dong Lin
Published: January 2017

A convenient rhodium(III)‐catalyzed cascade reaction of 7‐azaindoles and alkynes through multiple C−H bond activation for the synthesis of unique [5]azahelicenes has been developed. The optical property of these screw‐shaped helicene derivatives could be further utilized in electronic devices to recognize mercury ions.
Neue Queensferry Brücke in Schottland
Authors: Romberg Martin
Published: January 2017

Die neue Queensferry Brücke in Schottland in der Nähe von Edinburgh ist eine insgesamt 2 640 m lange Schrägkabelbrücke mit drei bis zu 210 m hohen Pylonen. Die beiden seilüberspannten Haupttragweiten sind 650 m, die beiden Seitenfelder 223 m und die Spannweiten der Vorlandbrücken sind bis zu 104 m lang. Die zwei Seilebenen sind mittig zwischen den beiden Fahrbahnen angeordnet und überlappen sich in der Mitte der Hauptöffnungen. Diese Besonderheit ist notwendig, um den Verbundüberbau und insbesondere den mittleren Pylon zu stabilisieren. Sowohl die Planung mit den damit verbundenen Nachweisen der außergewöhnlichen Bauzustände, wie z. B. dem mit zwei 322 m langen Kragarmen frei stehenden mittleren Pylon, als auch die Montage bei zum Teil äußerst widrigen Wetterbedingungen verlangten den beteiligten Ingenieuren und Arbeitern einiges ab. Aber nicht nur die Dimensionen und die Komplexität des Bauwerks machen diese Brücke auch für erfahrene Brückenbauer zu einer Besonderheit, sondern auch die Nähe zu den beiden bestehenden Brücken über den Firth of Forth. Dies sind zum einen die im Jahre 1890 eröffnete Forth Rail Bridge, die im Sommer 2015 in die UNESCO‐Weltkultur erbeliste aufgenommen wurde, als auch die Forth Road Bridge, eine im Jahre 1964 eröffnete Hängebrücke. Die drei Brücken aus drei verschiedenen Jahrhunderten werden nach Fertigstellung der Schrägseilbrücke eine einmalige Brückenkollektion bilden. Die Veröffentlichung fasst die Herausforderungen bei der Planung und Montage dieser einzigartigen Brücke zusammen. Einige Teile des Beitrags sind [4] entnommen, wo vor allem Aspekte der Bauausführung vertieft werden.
Overexpression and Functional Stabilization of Recombinant Human Lysophosphatidic Acid Receptor 1 Using an Amphiphatic Polymer
Authors: Han Seong‐Gu , Baek Seung‐Il , Lee Won‐Kyu , Sudakar Padmanaban , Yu Yeon Gyu
Published: January 2017

Human lysophosphatidic acid receptor 1 (LPA1
) is a G‐protein coupled receptor that mediates various biological functions such as proliferation, platelet aggregation, smooth muscle contraction, and tumor cell invasion. For dissection of the molecular function of LPA1
, a recombinant LPA1
was overexpressed in Escherichia coli membrane fractions and purified to homogeneity by single affinity chromatography. The purified LPA1
was stabilized with an amphiphilic polymer that was synthesized by the coupling of octylamine, glucosamine, and diethylaminoproylamine at the carboxylic groups of poly‐γ‐glutamic acid. The complex of purified LPA1
and amphiphilic polymer showed a monodisperse oligomer and specific binding to LPA with apparent Ki
values of 30 μM. Compared with the Gs protein, it also showed selective binding to the alpha subunit of the Gi protein. These results indicate that recombinant LPA1
in an amphiphilic polymer complex has an active conformation for interaction with ligands and G‐proteins.
Picoliter‐volume inkjet printing into planar microdevice reservoirs for low‐waste, high‐capacity drug loading
Authors: Fox Cade B. , Nemeth Cameron L. , Chevalier Rachel W. , Cantlon Joshua , Bogdanoff Derek B. , Hsiao Jeff C. , Desai Tejal A.
Published: January 2017

Oral delivery of therapeutics is the preferred route for systemic drug administration due to ease of access and improved patient compliance. However, many therapeutics suffer from low oral bioavailability due to low pH and enzymatic conditions, poor cellular permeability, and low residence time. Microfabrication techniques have been used to create planar, asymmetric microdevices for oral drug delivery to address these limitations. The geometry of these microdevices facilitates prolonged drug exposure with unidirectional release of drug toward gastrointestinal epithelium. While these devices have significantly enhanced drug permeability in vitro and in vivo, loading drug into the micron‐scale reservoirs of the devices in a low‐waste, high‐capacity manner remains challenging. Here, we use picoliter‐volume inkjet printing to load topotecan and insulin into planar microdevices efficiently. Following a simple surface functionalization step, drug solution can be spotted into the microdevice reservoir. We show that relatively high capacities of both topotecan and insulin can be loaded into microdevices in a rapid, automated process with little to no drug waste.
Tris(pentafluorophenyl)borane‐Catalyzed Reaction of Phosphorus/Boron and Nitrogen/Boron Frustrated Lewis Pair Dihydrogen Activation Products with Alkenes and Alkynes
Authors: Wang Tongdao , Jentgens Xenia , Daniliuc Constantin G. , Kehr Gerald , Erker Gerhard
Published: January 2017

The N/B frustrated Lewis pair (FLP) dihydrogen splitting product 10 undergoes a facile B(C6F5)3‐catalyzed regioselective trans‐1,2‐hydridoborate addition reaction to phenylacetylene to give the cis‐styryl‐containing ammonium/borate zwitterion 12. The B(C6F5)3‐catalyzed reaction of 10 with 1‐phenylpropyne proceeded analogously to give 13. The respective [B]/H− addition to styrene gave the corresponding [B]−CH2CH2Ph‐containing product 14 under mild conditions. We obtained evidence that the reaction is initiated by hydride migration between the two B centers involved and is then continued by hydride addition to the borane activated alkyne or alkene, respectively. The H2‐splitting product 4 derived from the ethylene‐bridged P/B FLP 3 reacted analogously with these alkynes and also with styrene under B(C6F5)3 catalysis to yield the respective alkenyl‐ or alkyl borate products. The new addition products were characterized by using XRD.
Site‐Selective Oxidative C4 Alkenylation of (NH)‐Pyrroles Bearing an Electron‐Withdrawing C2 Group
Authors: Laha Joydev K. , Bhimpuria Rohan A. , Mule Gajanan B.
Published: January 2017

A regioselective method for the oxidative C−H alkenylation of free (NH)‐pyrroles with various activated and unactivated alkenes to afford 4‐alkenylated (NH)‐pyrroles in good to excellent yields was explored. The key features that distinguish this method from those reported in the current literature include: 1)  The first report of the oxidative C4 alkenylation of (NH)‐pyrroles, 2) utilization of neutral conditions, 3) C2‐substituent‐controlled oxidative C4 alkenylation irrespective of the nature of the free (NH)‐pyrroles or N‐protected pyrroles used, 4) scope of using both electron‐deficient mono‐ and disubstituted alkenes and styrenes, and 5) synthesis of novel, enantiomerically pure 4‐alkenyl‐α‐methyl‐N‐benzylpyrroles bearing a stereocenter. An important application of this process to the synthesis of indoles through tandem C4/C5 double alkenylation followed by electrothermal cyclization was also examined.
Hollow Hierarchical Carbon Spheres Decorated with Ultrathin Molybdenum Disulfide Nanosheets as High‐Capacity Electrode Materials for Asymmetric Supercapacitors
Authors: Lin Tsung‐Wu , Hsiao Min‐Chien , Wang Ai‐Yin , Lin Jeng‐Yu
Published: January 2017

A hierarchically structured nanocomposite consisting of ultrathin MoS2 nanosheets densely dispersed on the surface of hollow carbon spheres (MoS2@HCS) is prepared through a glucose‐assisted, one‐pot synthesis. When evaluated as the cathode material for supercapacitors, MoS2@HCS exhibits pseudocapacitive behavior in a KOH electrolyte. More importantly, the capacitive performance of MoS2@HCS can be further boosted by activating the composite electrode in a KOH solution. The activation process partially removes the carbonaceous materials covering the MoS2 surface, which leads to more exposure of active electrode materials to the electrolyte. Activated MoS2@HCS exhibits a high specific capacitance value of 458 F g−1 at 1 A g−1, which is approximately 2.5 times higher than that of the MoS2 electrode. Furthermore, MoS2@HCS exhibits remarkable cycling stability, with a capacitance retention of about 86% over 1000 cycles at 8 A g−1. To further demonstrate the practical applications of composite electrode, an asymmetric supercapacitor device (ASC) is fabricated by using activated MoS2@HCS and reduced graphene oxide as the positive and the negative electrodes, respectively. The fabricated device delivers a maximum energy density of 13.7 Wh kg−1 at a power density of 616 W kg−1. Even at a high power density of 4.9 kW kg−1, the ASC device can still retain 80% of the maximum energy density.
AuI Iminophosphorane Complexes as Efficient Catalysts for the Cycloisomerization of Alkynyl Amides under Air, at Room Temperature, and in Aqueous or Eutectic‐Mixture Solutions
Authors: Rodríguez‐Álvarez María J. , Vidal Cristian , Schumacher Sören , Borge Javier , García‐Álvarez Joaquín
Published: January 2017

New iminophosphorane‐phosphine AuI complexes [AuCl(κ1‐P‐Ph2PCH2P{=NP(=S)(OR)2}Ph2)] (3 a,b) and [Au2Cl2(μ2‐P,S‐Ph2PCH2P{=NP(=S)(OR)2}Ph2)] (4 a,b) proved to be general, very efficient, and recyclable (up to four consecutive runs) catalysts for the cycloisomerization of alkynyl amides in water or choline chloride‐based eutectic mixtures as green solvents. Remarkably, this cycloisomerization reaction took place under mild conditions (low catalyst loading, at room temperature, and in the absence of cocatalysts or protecting atmosphere) to give the corresponding alkylidene lactams by employing an efficient and sustainable methodology.
A Concise Synthesis of Presilphiperfolane Core through a Tandem TMTU–Co‐Catalyzed Pauson–Khand Reaction and a 6π Electrocyclization Reaction (TMTU=Tetramethyl Thiourea)
Authors: Zhang Zichun , Li Yuanhe , Zhao Dandan , He Yingdong , Gong Jianxian , Yang Zhen
Published: January 2017

The synthesis of strained polycyclic systems from readily available precursors with a minimum number of steps and with regio‐ and stereochemical control constitutes an important synthetic challenge. Herein, we report a tandem reaction comprising Co–TMTU (tetramethyl thiourea)‐catalyzed Pauson–Khand (PK) and 6π‐electrocyclization reactions for the formation of the highly strained core of presilphiperfolanols. The developed chemistry has been applied to the total syntheses of 4‐epi‐presilphiperfolan‐8‐ol and 7‐epi‐presilphiperfolan‐1‐ol.
Proton‐Coupled Electron‐Transfer Processes in Ultrafast Time Domain: Evidence for Effects of Hydrogen‐Bond Stabilization on Photoinduced Electron Transfer
Authors: Dey Ananta , Dana Jayanta , Aute Sunil , Maity Partha , Das Amitava , Ghosh Hirendra N.
Published: January 2017

The proton‐coupled electron‐transfer (PCET) reaction is investigated for a newly synthesized imidazole‐anthraquinone biomimetic model with a photoactive RuII‐polypyridyl moiety that is covalently coupled to the imidazole fragment. Intramolecular H‐bonding interactions between imidazole and anthraquinone moieties favor the PCET process; this can be correlated to an appreciable positive shift in the one‐electron reduction potential of the coordinated anthraquinone moiety functionalized with the imidazole fragment. This can also be attributed to the low luminescence quantum yield of the RuII‐polypyridyl complex used. The dynamics of the intramolecular electron‐transfer (ET) and PCET processes are studied by using femtosecond transient absorption spectroscopy. The steady‐state spectroscopic studies and the results of the time‐resolved absorption studies confirm that H‐bonded water molecules play a major role in both ET and PCET dynamics as a proton relay in the excited state. The electron‐transfer process is followed by a change in the H‐bonding equilibrium between AQ and imidazole in acetonitrile solvent, and protonation of AQ.− by water leads to PCET in the presence of water. A slower forward and backward electron‐transfer rate is observed in the presence of D2O compared with that in H2O. These results provide further experimental support for a detailed understanding of the PCET process.
Preparation of a Salecan/poly(2‐acrylamido‐2‐methylpropanosulfonic acid‐co‐[2‐(methacryloxy)ethyl]trimethylammonium chloride) Semi‐IPN Hydrogel for Drug Delivery
Authors: Qi Xiaoliang , Li Junjian , Wei Wei , Su Ting , Zuo Gancheng , Pan Xihao , Zhang Jianfa , Dong Wei
Published: January 2017

Salecan is a water‐soluble bacterial polysaccharide consisting of glucopyranosyl units linked by α‐1,3 and β‐1,3 glycosidic bonds. salecan is suitable for the development of hydrogels for biomedical applications, given its outstanding physicochemical and biological profiles. In this study we designed a new semi‐interpenetrating polymer network hydrogel that introduces the salecan polysaccharide into a stimuli‐responsive poly(2‐acrylamido‐2‐methylpropanosulfonic acid‐co‐[2‐(methacryloxy)ethyl]trimethylammonium chloride) (PAM) hydrogel matrix for controlled insulin release. We found that salecan not only tunes the structure and pore size of the PAM hydrogels, but also endows them with adjustable water release rates. More importantly, in vitro drug loading/release assays demonstrated that insulin is efficiently loaded into the resulting hydrogels and can be released in an on‐demand manner by controlling the pH and salecan dose. Furthermore, cell viability and cell adhesion experiments verified the cell compatibility of these hydrogel carriers. Together, these results make salecan‐incorporated PAM hydrogels promising materials for drug delivery.
On the Shape of Compact Hypersurfaces with Almost‐Constant Mean Curvature
Authors: Ciraolo Giulio , Maggi Francesco
Published: January 2017

The distance of an almost‐constant mean curvature boundary from a finite family of disjoint tangent balls with equal radii is quantitatively controlled in terms of the oscillation of the scalar mean curvature. This result allows one to quantitatively describe the geometry of volume‐constrained stationary sets in capillarity problems.© 2017 Wiley Periodicals, Inc.
Optimal scheduling workflows in cloud computing environment using Pareto‐based Grey Wolf Optimizer
Authors: Khalili Azade , Babamir Seyed Morteza
Published: January 2017

A workflow consists of dependent tasks, and scheduling of a workflow in a cloud environment means the arrangement of tasks of the workflow on virtual machines (VMs) of the cloud. By increasing VMs and the diversity of task size, we have a huge number of such arrangements. Finding an arrangement with minimum completion time among all of the arrangements is an Non‐Polynomial‐hard problem. Moreover, the problem becomes more complex when a scheduling should consider a couple of conflicting objectives. Therefore, the heuristic algorithms have been paid attention to figure out an optimal scheduling. This means that although the single‐objective optimization, ie, minimizing completion time, proposes the workflow scheduling as an NP‐complete problem, multiobjective optimization for the scheduling problem is confronted with a more permutation space because an optimal trade‐off between the conflicting objectives is needed. To this end, we extended a recent heuristic algorithm called Grey Wolf Optimizer (GWO) and considered dependency graph of workflow tasks. Our experiment was carried out using the WorkflowSim simulator, and the results were compared with those of 2 other heuristic task scheduling algorithms.
Bioinspired Rose‐Petal‐Like Substrates Generated by Electropolymerization on Micropatterned Gold Substrates
Authors: Darmanin Thierry , Bombera Radoslaw , Colpo Pascal , Valsesia Andrea , Laugier Jean‐Pierre , Rossi François , Guittard Frédéric
Published: January 2017

Invited for this month's cover are the collaborating groups of Dr. Thierry Darmanin at Université Côte d'Azur, France and Dr. François Rossi at JRC European Commission, Italy. The cover picture shows a novel strategy for preparing substrates having a rose‐petal effect (high water adhesion). The micropatterning specifications (pillar diameter and pitch) and the electropolymerization parameters are key to obtaining both high water apparent contact angles and a high hysteresis. Read the full text of the article at 10.1002/cplu.201600387.
Coupling Reactions of Carbon Dioxide with Epoxides Catalyzed by Vanadium Aminophenolate Complexes
Authors: Elkurtehi Ali I. , Kerton Francesca M.
Published: January 2017

A series of vanadium compounds supported by tetradentate aminobis(phenolate) ligands were screened for catalytic reactivity in the reaction of propylene oxide (PO) with CO2: [VO(OMe)(O2NOBuMeMeth)], [VO(OMe)(ON2OBuMe)], [VO(OMe)(O2NNBuBuPy)], and [VO(OMe)(O2NOBuBuFurf)]. They showed similar reactivities, but reaction rates were higher for [VO(OMe)(ON2OBuMe)], which was studied in more detail. Turnover frequencies for conversion of PO over 500 h−1 were observed. Activation energies were determined experimentally through in situ IR spectroscopy for propylene carbonate (48.2 kJ mol−1), styrene carbonate (45.6 kJ mol−1), and cyclohexene carbonate (54.7 kJ mol−1) formation.
Synthesis of Cobalt Phosphide Nanoparticles Supported on Pristine Graphene by Dynamically Self‐Assembled Graphene Quantum Dots for Hydrogen Evolution
Authors: Wang Xiaoyan , Yuan Weiyong , Yu Yanan , Li Chang Ming
Published: January 2017

A highly active, durable, and low‐cost hydrogen evolution reaction (HER) catalyst is desirable for energy storage through water splitting but its fabrication presents great challenges. Herein, mediated by dynamically self‐assembled graphene quantum dots (GQDs), small, uniform, high‐density, and well‐dispersed CoP nanoparticles were grown in situ on pristine graphene for the first time. This hybrid nanostructure was then employed as HER electrocatalyst, showing an onset potential of 7 mV, an overpotential of 91.3 mV to achieve 10 mA cm−2, a Tafel slope of 42.6 mV dec−1, and an exchange current density of 0.1225 mA cm−2, all of which compare favorably to those of most reported non‐noble‐metal catalysts. The developed catalyst also exhibits excellent durability with negligible current loss after 2000 cyclic voltammetry cycles (+0.01 to −0.17 V vs. RHE) or 34 h of chronoamperometric measurement at an overpotential of 91.3 mV. This work not only develops a new strategy for the fabrication of high‐performance and inexpensive electrocatalysts for HER but also provides scientific insight into the mechanism of the dynamically self‐assembled GQDsmediated synthesis process.
NHC‐Ag/Pd‐Catalyzed Reductive Carboxylation of Terminal Alkynes with CO2 and H2: A Combined Experimental and Computational Study for Fine‐Tuned Selectivity
Authors: Yu Dingyi , Zhou Feng , Lim Diane S. W. , Su Haibin , Zhang Yugen
Published: January 2017

Reductive carboxylation of terminal alkynes utilizing CO2 and H2 as reactants is an interesting and challenging transformation. Theoretical calculations indicated it would be kinetically possible to obtain cinnamic acid, the reductive carboxylation product, from phenylacetylene in a CO2/H2 system with an N‐heterocyclic carbene (NHC)‐supported Ag/Pd bimetallic catalysts through competitive carboxylation/hydrogenation cascade reactions in one step. These calculations were verified experimentally with a poly‐NHC‐supported Ag/Pd catalyst. By tuning the catalyst composition and reaction temperature, phenylacetylene was selectively converted to cinnamic acid, hydrocinnamic acid, or phenylpropiolic acid in excellent yields.
High‐efficiency transformerless buck–boost DC–DC converter
Authors: Banaei Mohamad Reza , Ajdar Faeghi Bonab Hossein
Published: January 2017

A novel high‐efficiency transformerless buck–boost DC–DC converter is proposed in this paper. The presented converter voltage gain is higher than that of the conventional boost, buck–boost, CUK, SEPIC and ZETA converters, and high voltage gain can be obtained with a suitable duty cycle. The voltage stress across the power switch is low. Hence, the low on‐state resistance of the power switch can be selected to decrease conduction loss of the switch and improve efficiency. The input current ripple in the presented converter is low. The principle of operation and the mathematical analyses of the proposed converter are explained. The validity of the presented converter is verified by the simulation results in PSCAD/EMTDC software and experimental results based on the prototype circuit with 250 W and 40 kHz. Copyright © 2017 John Wiley & Sons, Ltd.
Activated Platelet‐Derived and Leukocyte‐Derived Circulating Microparticles and the Risk of Thrombosis in Heparin‐Induced Thrombocytopenia: A Role for PF4‐Bearing Microparticles?
Authors: Campello Elena , Radu Claudia M. , Duner Elena , Lombardi Anna M. , Spiezia Luca , Bendo Raffaele , Ferrari Silvia , Simioni Paolo , Fabris Fabrizio
Published: January 2017

Background

Though the presence of platelets‐derived microparticles (MPs) have previously been described in heparin‐induced thrombocytopenia (HIT), the mechanism of thrombosis in HIT remains poorly understood. We aimed to assess the presence and origin of MPs in patients with HIT and their possible contribution to HIT with thrombosis (HITT).

Methods

Forty‐five patients with HIT and 45 matched hospitalized patients with not confirmed HIT (HIT‐negative) were enrolled. Twelve HIT patients (27%) developed HITT. MPs expressing phosphatidylserine (Annexin V‐MP), activated platelet‐derived (P‐Selectin+), activated leukocyte‐derived (L‐Selectin+), PF4‐bearing and tissue factor‐bearing (TF+) MPs were measured by flow‐cytometry.

Results

HIT patients showed significantly higher median levels of P‐Selectin+, L‐Selectin+, PF4‐bearing, L‐Selectin+/TF + MPs than HIT‐negative; PF4‐bearing MP showed the highest statistical difference. As compared to HIT patients, HITT patients showed a trend of higher median levels of all MP subtypes considered but the differences were not statistically significant. Only levels of activated‐leukocyte/TF + MPs (L‐Selectin + CD142+) were significantly higher (P = 0.015). Sensitive analyses showed that HIT patients with activated‐leukocyte/TF + MPs above the cut‐off (52 MP/µL) had an odds ratio (OR) for thrombosis of 3.78 (95%CI, 0.98–14.5, P = 0.045). The combination of activated‐leukocyte/TF + MPs and PF4‐bearing‐MPs above the cut‐off (1416 MP/uL) resulted in a higher risk of HITT (OR 4.49 (95% CI, 1.17–8.05, P = 0.014).

Conclusions

We showed for the first time the presence of circulating PF4‐bearing MPs derived from activated platelets in patients with HIT; activated leukocyte/TF + MPs are associated with an increased thrombotic risk. Our findings confirm that HIT antibodies complexes may determine a TF‐driven prothrombotic state through the activation of platelets and leukocytes. © 2017 International Clinical Cytometry Society
Identifying the moderating effect of trust on the adoption of cloud‐based services
Authors: Rahi Shiromani Balmukund , Bisui Sandip , Misra Subhas Chandra
Published: January 2017

Cloud computing provides a way to coordinate and share relevant information and data on real‐time basis over an organization. The adoption of cloud services is one of the most emerging technological advances in the practice of current competitive business environment. The research done in this article is based on the analysis of the data obtained from the semiconductor sector. Cloud adoption would most likely be the best answer for them. However, because of various types of complexities, semiconductor industries may have to confront with a few trust issues while receiving cloud services. This article aims to identify the trust factors in the adoption of cloud services in semiconductor industries. Further, the moderating effect of these trust elements related to the technological, organizational, and environmental success factors has been discussed here. On the basis of literature survey, a hypothetical model has been developed, and the relationships among the latent variables have been studied by using structural equations. The study reveals that while trust factors moderate the technology and environment‐related success factors, there is not much moderating effect of the trust issues on the organization‐related success factors in the adoption of cloud services in semiconductor industries.
Cross‐species analysis of the canine and human bladder cancer transcriptome and exome
Authors: Ramsey Stephen A. , Xu Tanjin , Goodall Cheri , Rhodes Adelaide C. , Kashyap Amita , He Jun , Bracha Shay
Published: January 2017

We investigated the correspondence between transcriptome and exome alterations in canine bladder cancer and the correspondence between these alterations and cancer‐driving genes and transcriptional alterations in human bladder cancer. We profiled canine bladder tumors using mRNA‐seq and exome‐seq in order to investigate the similarity of transcriptional alterations in bladder cancer, in humans and canines, at the levels of gene functions, pathways, and cytogenetic regions. We found that the transcriptomes of canine and human bladder cancer are remarkably similar at the functional and pathway levels. We demonstrated that canine bladder cancer involves coordinated differential expression of genes within cytogenetic bands, and that these patterns are consistent with those seen in human bladder cancer. We found that genes that are mutated in canine bladder cancer are more likely to be transcriptionally downregulated than non‐mutated genes, in the tumor. Finally we report three novel mutations (FAM133B, RAB3GAP2, and ANKRD52) for canine bladder cancer.
Correspondent Functional Topography of the Human Left Inferior Parietal Lobule at Rest and Under Task Revealed Using Resting‐State fMRI and Coactivation Based Parcellation
Authors: Wang Jiaojian , Xie Sangma , Guo Xin , Becker Benjamin , Fox Peter T. , Eickhoff Simon B. , Jiang Tianzi
Published: January 2017

The human left inferior parietal lobule (LIPL) plays a pivotal role in many cognitive functions and is an important node in the default mode network (DMN). Although many previous studies have proposed different parcellation schemes for the LIPL, the detailed functional organization of the LIPL and the exact correspondence between the DMN and LIPL subregions remain unclear. Mounting evidence indicates that spontaneous fluctuations in the brain are strongly associated with cognitive performance at the behavioral level. However, whether a consistent functional topographic organization of the LIPL during rest and under task can be revealed remains unknown. Here, they used resting‐state functional connectivity (RSFC) and task‐related coactivation patterns separately to parcellate the LIPL and identified seven subregions. Four subregions were located in the supramarginal gyrus (SMG) and three subregions were located in the angular gyrus (AG). The subregion‐specific networks and functional characterization revealed that the four anterior subregions were found to be primarily involved in sensorimotor processing, movement imagination and inhibitory control, audition perception and speech processing, and social cognition, whereas the three posterior subregions were mainly involved in episodic memory, semantic processing, and spatial cognition. The results revealed a detailed functional organization of the LIPL and suggested that the LIPL is a functionally heterogeneous area. In addition, the present study demonstrated that the functional architecture of the LIPL during rest corresponds with that found in task processing. Hum Brain Mapp 38:1659–1675, 2017. © 2017 Wiley Periodicals, Inc.
Impact of correction factors in human brain lesion‐behavior inference
Authors: Sperber Christoph , Karnath Hans‐Otto
Published: January 2017

Statistical voxel‐based lesion‐behavior mapping (VLBM) in neurological patients with brain lesions is frequently used to examine the relationship between structure and function of the healthy human brain. Only recently, two simulation studies noted reduced anatomical validity of this method, observing the results of VLBM to be systematically misplaced by about 16 mm. However, both simulation studies differed from VLBM analyses of real data in that they lacked the proper use of two correction factors: lesion size and “sufficient lesion affection.” In simulation experiments on a sample of 274 real stroke patients, we found that the use of these two correction factors reduced misplacement markedly compared to uncorrected VLBM. Apparently, the misplacement is due to physiological effects of brain lesion anatomy. Voxel‐wise topographies of collateral damage in the real data were generated and used to compute a metric for the inter‐voxel relation of brain damage. “Anatomical bias” vectors that were solely calculated from these inter‐voxel relations in the patients' real anatomical data, successfully predicted the VLBM misplacement. The latter has the potential to help in the development of new VLBM methods that provide even higher anatomical validity than currently available by the proper use of correction factors. Hum Brain Mapp 38:1692–1701, 2017. © 2017 Wiley Periodicals, Inc.
On the dependence of response inhibition processes on sensory modality
Authors: Bodmer Benjamin , Beste Christian
Published: January 2017

The ability to inhibit responses is a central sensorimotor function but only recently the importance of sensory processes for motor inhibition mechanisms went more into the research focus. In this regard it is elusive, whether there are differences between sensory modalities to trigger response inhibition processes. Due to functional neuroanatomical considerations strong differences may exist, for example, between the visual and the tactile modality. In the current study we examine what neurophysiological mechanisms as well as functional neuroanatomical networks are modulated during response inhibition. Therefore, a Go/NoGo‐paradigm employing a novel combination of visual, tactile, and visuotactile stimuli was used. The data show that the tactile modality is more powerful than the visual modality to trigger response inhibition processes. However, the tactile modality loses its efficacy to trigger response inhibition processes when being combined with the visual modality. This may be due to competitive mechanisms leading to a suppression of certain sensory stimuli and the response selection level. Variations in sensory modalities specifically affected conflict monitoring processes during response inhibition by modulating activity in a frontal parietal network including the right inferior frontal gyrus, anterior cingulate cortex and the temporoparietal junction. Attentional selection processes are not modulated. The results suggest that the functional neuroanatomical networks involved in response inhibition critically depends on the nature of the sensory input. Hum Brain Mapp 38:1941–1951, 2017. © 2017 Wiley Periodicals, Inc.
The CAN‐In network: A biologically inspired model for self‐sustained theta oscillations and memory maintenance in the hippocampus
Authors: Giovannini Francesco , Knauer Beate , Yoshida Motoharu , Buhry Laure
Published: January 2017

During working memory tasks, the hippocampus exhibits synchronous theta‐band activity, which is thought to be correlated with the short‐term memory maintenance of salient stimuli. Recent studies indicate that the hippocampus contains the necessary circuitry allowing it to generate and sustain theta oscillations without the need of extrinsic drive. However, the cellular and network mechanisms supporting synchronous rhythmic activity are far from being fully understood. Based on electrophysiological recordings from hippocampal pyramidal CA1 cells, we present a possible mechanism for the maintenance of such rhythmic theta‐band activity in the isolated hippocampus. Our model network, based on the Hodgkin‐Huxley formalism, comprising pyramidal neurons equipped with calcium‐activated nonspecific cationic (CAN) ion channels, is able to generate and sustain synchronized theta oscillations (4–12 Hz), following a transient stimulation. The synchronous network activity is maintained by an intrinsic CAN current (ICAN), in the absence of constant external input. When connecting the pyramidal‐CAN network to fast‐spiking inhibitory interneurons, the dynamics of the model reveal that feedback inhibition improves the robustness of fast theta oscillations, by tightening the synchronization of the pyramidal CAN neurons. The frequency and power of the theta oscillations are both modulated by the intensity of the ICAN, which allows for a wide range of oscillation rates within the theta band. This biologically plausible mechanism for the maintenance of synchronous theta oscillations in the hippocampus aims at extending the traditional models of septum‐driven hippocampal rhythmic activity. © 2017 Wiley Periodicals, Inc.
PUBLIC POLICY, CHILD DEVELOPMENT RESEARCH AND BOYS AT RISK: CHALLENGING, ENDURING AND NECESSARY PARTNERSHIP
Authors: Mckinney Marvin , Fitzgerald Hiram E. , Winn Donna‐Marie , Babcock Patrick
Published: January 2017

Research findings documenting the issues and challenges of boys prebirth through age 5 years have barely penetrated the arena of public policy making nor has it permeated the public agenda of politicians, government, or other funding stakeholders. The purpose of this article is to articulate pathways for researchers to enter into the policy‐making process. We review critical issues related to implementing the process of public policy. We argue that the policy process needs to be informed by more dynamic theoretical models of human development, and that researchers and clinicians need to be exposed more deeply to the processes required to inform and subsequently change public policy. We contend that most quantitative research on boys at risk occurs at the micro‐ and the mesosystem level rather than at the exo‐ and the macrosystem levels where structural societal policies embedded in economic and racial inequities contribute to risk. Researchers, clinicians, and policy makers need to create collaborative partnerships designed to develop, advocate, and implement more evidence‐based policies designed to enhance the quality of life for boys at risk.