bluuebunny/crossref_metadata_2025 huggingface dataset:
Application of the PrimRglo Assay Chemistry to Multiplexed Bead Assays
Authors: Fang Liang , Weis Anna , Wong Lawrence Kurniawan , Yeh David Che‐Cheng , Lai Richard , Corrie Simon , Barnard Ross T.
Published: July 2014

In this unit, we describe a multiplex microsphere quantitative PCR. The system is based on the use of two additional oligonucleotides within a single tube PCR reaction. The first oligonucleotide is modified with a single base pair mismatch and is otherwise equivalent to a universal sequence added to the forward PCR primer. Further, this first extra oligonucleotide is coupled to Luminex microspheres. The second additional oligonucleotide is designed to be complementary to the universal sequence, and is modified with the fluorescent dye Cy3. As the PCR reaction proceeds, the second oligonucleotide is able to bind to the microspheres. Thus, quantitative monitoring of PCR progress takes place. The microsphere‐mediated Cy3‐detection is measured using flow cytometry directly after the PCR reaction. This allows a flow cytometer analysis from up to 150 different spheres and, therefore, multiple genes in one reaction. The multiplex microsphere qPCR is demonstrated using three target genes from Influenza A and Neisseria meningitidis. The multiplex microsphere system will enable a higher degree of multiplexing than is possible with currently available qPCR systems. Curr. Protoc. Cytom. 69:13.13.1‐13.13.10. © 2014 by John Wiley & Sons, Inc.
3‐D Seismic Surveys Explore German Petrothermal Reserves
Authors: Lüschen Ewald , Schulz Rüdiger
Published: July 2014

Three‐dimensional (3‐D) seismic reflection techniques are now an indispensable tool for locating and characterizing sites for building geothermal power plants. The techniques not only work when imaging layered sediments but can also pinpoint geothermal sources in crystalline environments such as granite.
Sentinel Satellites Initiate New Era in Earth Observation
Authors: Showstack Randy
Published: July 2014

With the European Space Agency's (ESA) Sentinel‐1A satellite expected to enter into its operational phase later this summer, it ushers in a new series of Earth observation satellites. The first generation of the fleet of satellites, which will total 20 when all are launched, will comprise “the most comprehensive Earth observation system worldwide,” according to Josef Aschbacher, head of program planning and coordination for ESA's Earth Observation Programs directorate. The satellites are a key part of Copernicus, the European Earth Observation Program that from 1998 to 2012 was called the Global Monitoring for Environment and Security (GMES) program.
2014 AGU Union Medalists, Awardees, and Prize Recipient Announced
Authors: Finn Carol , McKenzie Judith Ann
Published: July 2014

On behalf of the Honors and Recognition Committee and the Union award selection committees, we are very pleased to present the 2014 AGU Union medals, awards, and prize recipients. We honor these individuals, whose passion for scientific excellence and outstanding achievements in advancing and communicating science significantly contribute to a better future for us all. Their work truly embodies AGU's vision to “advance and communicate science and its power to ensure a sustainable future.”
First depth measurements taken for extraterrestrial lake
Authors: Wendel JoAnna
Published: July 2014

Since 2004, NASA's Cassini mission has been orbiting Saturn and taking measurements of the planet itself as well as its largest moon, Titan, which has an atmosphere that can serve as an analog for a young Earth. During Cassini's flyby of Titan in May 2013, it collected data from the moon's second‐largest sea, Ligeia Mare.
Field evidence of the viscous sublayer in a tidally forced developing boundary layer
Authors: Wengrove M. E. , Foster D. L.
Published: July 2014

Field observations of boundary layer development within a tidally forced estuary revealed evidence of an observable viscous sublayer. Evidence is provided by several independent measures of the flow field, including hydrodynamic smoothness, an immobile bed, and characteristic velocity, constant stress, and higher‐order moment structures. This investigation reports what may be the second comprehensive observation of the viscous sublayer in a marine environment, and what could be the first observation of a momentum balance that includes the viscous sublayer within a shallow estuarine environment. Hydrodynamic observations were made in a straight channel within the Great Bay Estuary of New Hampshire over a flat sandy mud with low water depth of 1.5 m at the sampling location. Beyond quantifying the role of the benthic boundary layer in nutrient dynamics, these observations are useful to provide insight into very near boundary stress estimates leading to incipient motion in estuarine and coastal environments.
Surface and free tropospheric sources of methanesulfonic acid over the tropical Pacific Ocean
Authors: Zhang Yuzhong , Wang Yuhang , Gray Burton Alonza , Gu Dasa , Mauldin Lee , Cantrell Christopher , Bandy Alan
Published: July 2014

The production of sulfate aerosols through sulfur chemistry in marine environments is critical to the tropical climate system. However, not all sulfur compounds have been studied in detail. One such compound is methanesulfonic acid (MSA). In this study, we use a one‐dimensional chemical transport model to analyze the observed vertical profiles of gas phase MSA during the Pacific Atmospheric Sulfur Experiment. The observed sharp decrease in MSA from the surface to 600 m implies a surface source of 4.0 × 107 molecules/cm2/s. Evidence suggests that this source is photolytically enhanced in daytime. We also find that the observed large increase of MSA from the boundary layer into the lower free troposphere (1000–2000 m) results mainly from the degassing of MSA from dehydrated aerosols. We estimate a source of 1.2 × 107 molecules/cm2/s to the free troposphere through this pathway. This source of soluble MSA could potentially provide an important precursor for new particle formation in the free troposphere over the tropics, affecting the climate system through aerosol‐cloud interactions.
Mechanisms of time‐dependent deformation in porous limestone
Authors: Brantut Nicolas , Heap Michael J. , Baud Patrick , Meredith Philip G.
Published: July 2014

We performed triaxial deformation experiments on a water‐saturated porous limestone under constant strain rate and constant stress (creep) conditions. The tests were conducted at room temperature and at low effective pressures Peff=10 and Peff=20 MPa, in a regime where the rock is nominally brittle when tested at a constant strain rate of 10−5 s−1. Under these conditions and at constant stress, the phenomenon of brittle creep occurs. At Peff=10 MPa, brittle creep follows similar trends as those observed in other rock types (e.g., sandstones and granites): only small strains are accumulated before failure, and damage accumulation with increasing strain (as monitored by P wave speeds measurements during the tests) is not strongly dependent on the applied stresses. At Peff=20 MPa, brittle creep is also macroscopically observed, but when the creep strain rate is lower than ≈10−7 s−1, we observe that (1) much larger strains are accumulated, (2) less damage is accumulated with increasing strain, and (3) the deformation tends to be more compactant. These observations can be understood by considering that another deformation mechanism, different from crack growth, is active at low strain rates. We explore this possibility by constructing a deformation mechanism map that includes both subcritical crack growth and pressure solution creep processes; the increasing contribution of pressure solution creep at low strain rates is consistent with our observations.
Satellite views of the episodic terrestrial material transport to the southern Okinawa Trough driven by typhoon
Authors: He Xianqiang , Bai Yan , Chen Chen‐Tung Arthur , Hsin Yi‐Chia , Wu Chau‐Ron , Zhai Weidong , Liu Zhiliang , Gong Fang
Published: July 2014

Using satellite‐derived water transparency (alias Secchi depth) images, we found clear signals of terrestrial material transport to the southern Okinawa Trough triggered by the Typhoon Morakot in August 2009. Three sources were identified: one is from the eastern coast of Taiwan, another is from the western coast of Taiwan, and the other is from the coast of mainland China. Carried by northward flows, typhoon‐triggered terrestrial materials from both sides of Taiwan's coasts were transported to the region northeast of Taiwan. Moreover, the terrestrial material from the coast of mainland China could cross the Taiwan Strait and be further transported to the region northeast of Taiwan. These typhoon‐induced terrestrial materials off northeastern Taiwan could then be transported to the southern Okinawa Trough along the western edge of the Kuroshio. In addition to the particulate terrestrial material transported, nutrients might also be transported to the Kuroshio main stream. A significant phytoplankton bloom was observed along the Kuroshio path for about 300 km off northeast of Taiwan. Our results indicate that episodic cyclone‐driven terrestrial material transport could be another source of mud in the southern Okinawa Trough.
Summer primary productivity and phytoplankton community composition driven by different hydrographic structures in the East/Japan Sea and the Western Subarctic Pacific
Authors: Kwak Jung Hyun , Lee Sang Heon , Hwang Jeomshik , Suh Young‐Sang , Je Park Hyun , Chang Kyung‐Il , Kim Kyung‐Ryul , Kang Chang‐Keun
Published: July 2014

The East/Japan Sea (EJS) is a highly productive marginal sea in the northwest Pacific, consisting of three basins (Ulleung Basin: UB, Yamato Basin: YB, and Japan Basin: JB). To find causes of the reportedly high primary productivity in summer in the EJS, especially in the UB, we measured primary productivity, phytoplankton composition, and other environmental variables. The water column was strongly stratified in the EJS compared with the Western Subarctic Pacific (WSP). Integrated primary productivity was two times higher in the EJS (612 mg C m−2 d−1) than in the WSP (291 mg C m−2 d−1). The vertical distributions of physicochemical and biological factors confirmed that production in the subsurface chlorophyll maximum layer in the study regions was an important factor regulating primary productivity within the water column. While picoplankton (<2.7 µm) dominated in the WSP, JB, and YB, micro/nanoplankton (≥2.7 µm) dominated in the UB. Contribution by picoplankton to total biomass and primary productivity in the UB was significantly lower than in the other regions. CHEMTAX analysis using marker pigments showed that diverse phytoplankton groups inhabited the study regions. Cluster and canonical correspondence analyses showed high correlation between the spatial variation in phytoplankton assemblages with the water mass properties mainly represented by water temperature and nitrate concentration. Overall, our results suggest that the hydrographic structure of water column in the study region is an important controlling factor of the biomass and productivity of phytoplankton as well as their diversity in size and taxonomic groups.
Long‐term trends in the East Australian Current separation latitude and eddy driven transport
Authors: Cetina‐Heredia P. , Roughan M. , van Sebille E. , Coleman M. A.
Published: July 2014

An observed warming of the Tasman Sea in recent decades has been linked to a poleward shift of the maximum wind stress curl, and a strengthening of the poleward flow along the coast of southeastern Australia. However, changes in the East Australian Current (EAC) separation latitude, as well as in the contribution of the EAC, the EAC extension and its eddy field to the total southward transport due to such a strengthening remain unknown. This study uses 30 years (1980–2010) of the Ocean Forecast for the Earth Simulator (OFES) sea surface height and velocity outputs to obtain a three decade long‐time series of (i) the EAC separation latitude, (ii) the southward transport along the coast of southeastern Australia (28°S–39°S), and (iii) the southward transport across the EAC separation latitude. A Lagrangian approach is implemented and the spin parameter Ω is used to provide a quantitative distinction between the transports occurring outside and inside (cyclonic and anticyclonic) eddies. Significant positive trends of the low pass southward transports indicate that the intensification of the poleward flow has occurred both within the EAC and in the EAC extension. In addition, a significant increase in southward transport inside and outside eddies is found. Importantly, the contribution of eddy driven transport has a large temporal variability and shows a sharp increase from 2005 onward. Finally our results show that the EAC has not penetrated further south but it has separated more frequently at the southernmost latitudes within the region where it typically turns eastward.
A national‐scale assessment of long‐term water budget closures for Canada's watersheds
Authors: Wang Shusen , McKenney Daniel W. , Shang Jiali , Li Junhua
Published: July 2014

This study examined the long‐term water budget closures for 370 watersheds over Canada's landmass by using 30 years' (1981–2010) data products recently produced for precipitation (P) gridded using climate station measurements, land surface evapotranspiration (ET), and water surface evaporation (E0) obtained by the Ecological Assimilation of Land and Climate Observations (EALCO) model, and observed streamflow (Q). The results show that 29%, 58%, and 83% of the watersheds were closed within 5%, 10%, and 20% of P, respectively. The positive and negative imbalances among the 370 watersheds are largely offset and the national scale average is −24 mm yr−1, or 4.2% of P. Water budget closures have large variation across the landmass. Regions with sparse or less accurate monitoring of P such as the mountainous region and the Arctic exhibit the largest water imbalances. Further efforts on enhancing the climate observation networks, improving spatial models for P and ET estimates, and streamflow measurements are all likely critical for a better understanding of Canada's water budgets.
A discrete‐time indirect adaptive multiple‐model actuator failure compensation scheme
Authors: Tan Chang , Tao Gang , Qi Ruiyun
Published: July 2014

A new discrete‐time actuator failure compensation control scheme is developed, using a multiple‐model adaptive control approach which has the capacity to achieve faster and more accurate compensation of failure uncertainties. An individual adaptive system, for each possible failure pattern in a failure pattern set of interest for compensation, is designed using an indirect model reference adaptive control scheme for actuator failure compensation. A multiple‐model control switching mechanism for discrete‐time systems is set up by finding the minimal performance index to select the most appropriate control law. The performance indices are based on the adaptive estimation errors of individual parameterized systems with actuator failures. Simulation results from an aircraft flight control system example are presented to show the desired closed‐loop system stability and tracking performance despite the presence of uncertain actuator failures. Copyright © 2014 John Wiley & Sons, Ltd.
Near‐Field Analysis of Bright and Dark Modes on Plasmonic Metasurfaces Showing Extraordinary Suppressed Transmission
Authors: Dobmann Sabine , Kriesch Arian , Ploss Daniel , Peschel Ulf
Published: July 2014

Plasmonic metasurfaces are investigated that consist of a sub‐wavelength line pattern in an ultrathin (∼10 nm) silver film, designed for extraordinary suppressed transmission (EOST) in the visible spectral range. Measurements with a near‐field scanning optical microscope (NSOM) demonstrate that far‐field irradiation resonantly excites antenna‐like (bright) modes that are localized on the metal ridges. The re‐radiation of these modes into the far‐field interferes destructively with the transmitted wave, thus suppressing transmission almost completely. In contrast, a second type of mode, bound (dark) surface plasmon polaritons (SPPs) launched from an NSOM tip, propagates well across the metasurface, preferentially perpendicular to the grating lines.
Inability to consent does not diminish the desirability of stroke thrombolysis
Authors: Chiong Winston , Kim Anthony S. , Huang Ivy A. , Farahany Nita A. , Josephson S. Andrew
Published: July 2014

Objective

Some have argued that physicians should not presume to make thrombolysis decisions for incapacitated patients with acute ischemic stroke because the risks and benefits of thrombolysis involve deeply personal values. We evaluated the influence of the inability to consent and of personal health‐related values on older adults' emergency treatment preferences for both ischemic stroke and cardiac arrest.

Methods

A total of 2,154 US adults age ≥50 years read vignettes in which they had either suffered an acute ischemic stroke and could be treated with thrombolysis, or had suffered a sudden cardiac arrest and could be treated with cardiopulmonary resuscitation. Participants were then asked (1) whether they would want the intervention, or (2) whether they would want to be given the intervention even if their informed consent could not be obtained. We elicited health‐related values as predictors of these judgments.

Results

Older adults were as likely to want stroke thrombolysis when unable to consent (78.1%) as when asked directly (76.2%), whereas older adults were more likely to want cardiopulmonary resuscitation when unable to consent (83.6% compared to 75.9%). Greater confidence in the medical system and reliance on statistical information in decision making were both associated with desiring thrombolysis.

Interpretation

Older adults regard thrombolysis no less favorably when considering a situation in which they are unable to consent. These findings provide empirical support for recent professional society recommendations to treat ischemic stroke with thrombolysis in appropriate emergency circumstances under a presumption of consent. Ann Neurol 2014;76:296–304
A Single‐Site Platinum CO Oxidation Catalyst in Zeolite KLTL: Microscopic and Spectroscopic Determination of the Locations of the Platinum Atoms
Authors: Kistler Joseph D. , Chotigkrai Nutchapon , Xu Pinghong , Enderle Bryan , Praserthdam Piyasan , Chen Cong‐Yan , Browning Nigel D. , Gates Bruce C.
Published: July 2014

A stable site‐isolated mononuclear platinum catalyst with a well‐defined structure is presented. Platinum complexes supported in zeolite KLTL were synthesized from [Pt(NH3)4](NO3)2, oxidized at 633 K, and used to catalyze CO oxidation. IR and X‐ray absorption spectra and electron micrographs determine the structures and locations of the platinum complexes in the zeolite pores, demonstrate the platinum‐support bonding, and show that the platinum remained site isolated after oxidation and catalysis.
Precision PEGylated Polymers Obtained by Sequence‐Controlled Copolymerization and Postpolymerization Modification
Authors: Srichan Sansanee , Mutlu Hatice , Badi Nezha , Lutz Jean‐François
Published: July 2014

Copolymers containing water‐soluble poly(ethylene glycol) (PEG) side chains and precisely controlled functional microstructures were synthesized by sequence‐controlled copolymerization of donor and acceptor comonomers, that is, styrene derivatives and N‐substituted maleimides. Two routes were compared for the preparation of these structures: a) the direct use of a PEG–styrene macromonomer as a donor comonomer, and b) the use of an alkyne‐functionalized styrenic comonomer, which was PEGylated by copper‐catalyzed alkyne–azide cycloaddition after polymerization. The latter method was found to be the most versatile and enabled the synthesis of high‐precision copolymers. For example, PEGylated copolymers containing precisely positioned fluorescent (e.g. pyrene), switchable (e.g. azobenzene), and reactive functionalities (e.g. an activated ester) were prepared.
pH‐Dependent Proton Conducting Behavior in a Metal–Organic Framework Material
Authors: Phang Won Ju , Lee Woo Ram , Yoo Kicheon , Ryu Dae Won , Kim BongSoo , Hong Chang Seop
Published: July 2014

A porous metal–organic framework (MOF), [Ni2(dobdc)(H2O)2]⋅6 H2O (Ni2(dobdc) or Ni‐MOF‐74; dobdc4−=2,5‐dioxido‐1,4‐benzenedicarboxylate) with hexagonal channels was synthesized using a microwave‐assisted solvothermal reaction. Soaking Ni2(dobdc) in sulfuric acid solutions at different pH values afforded new proton‐conducting frameworks, H+@Ni2(dobdc). At pH 1.8, the acidified MOF shows proton conductivity of 2.2×10−2 S cm−1 at 80 °C and 95 % relative humidity (RH), approaching the highest values reported for MOFs. Proton conduction occurs via the Grotthuss mechanism with a significantly low activation energy as compared to other proton‐conducting MOFs. Protonated water clusters within the pores of H+@Ni2(dobdc) play an important role in the conduction process.
Controlling the Orientation of Nanowrinkles and Nanofolds by Patterning Strain in a Thin Skin Layer on a Polymer Substrate
Authors: Huntington Mark D. , Engel Clifford J. , Odom Teri W.
Published: July 2014

We describe herein how to control the orientation of polymer nanowrinkles and nanofolds with large amplitudes. Nanowrinkles were created by chemically treating thermoplastic polystyrene sheets to form a thin skin layer and then heating the substrate to relieve strain. By manipulating the strain globally and locally in the skin layer, we could tune whether wrinkles or folds formed, as well as the distances over which these structures could be produced. This unique materials system provided access to high strain regimes, which enabled mechanisms behind the spontaneous formation of complex structures to be explored.
Direct Asymmetric Mannich‐Type Reaction of α‐Isocyanoacetates with Ketimines using Cinchona Alkaloid/Copper(II) Catalysts
Authors: Hayashi Masashi , Iwanaga Masaru , Shiomi Noriyuki , Nakane Daisuke , Masuda Hideki , Nakamura Shuichi
Published: July 2014

The enantioselective direct Mannich‐type reaction of ketimines with α‐isocyanoacetates has been developed. Excellent yields and enantioselectivity were observed for the reaction of various ketimines and α‐isocyanoacetates using cinchona alkaloid/Cu(OTf)2 and a base. Both enantiomers of the products could be obtained by using pseudoenantiomeric chiral catalysts. This process offers an efficient route for the synthesis of α,β‐diamino acids.
Dikalium‐1,1′‐dinitramino‐5,5′‐bistetrazolat – ein Primärsprengstoff mit schneller Detonation und hoher Initiierungsleistung
Authors: Fischer Dennis , Klapötke Thomas M. , Stierstorfer Jörg
Published: July 2014

Ausreichend leistungsfähige Primärsprengstoffe wie Bleiazid basieren oft auf giftigen Schwermetallen, die es zu ersetzen gilt. Eine neue potenziell geeignete Verbindung, Dikalium‐1,1′‐dinitramino‐5,5′‐bistetrazolat (K2DNABT), wurde ausgehend von Dimethylcarbonat, Hydrazin und Glyoxal hergestellt und chemisch (z. B. durch Röntgenkristallstruktur‐ und Elementaranalyse sowie NMR‐ und Schwingungsspektroskopie) sowie auf ihre physikochemischen Eigenschaften (z. B. auf Reibe‐, Schlag‐, elektrostatische Empfindlichkeit und thermische Stabilität) hin analysiert. K2DNABT zeigt eine geeignete thermische und mechanische Stabilität zur Verwendung als Primärsprengstoff. Die hohe Dichte (2.11 g cm−3) und Bildungswärme (326 kJ mol−1) resultieren in einer hohen berechneten Detonationsgeschwindigkeit (8330 m s−1) und einem hohen Detonationsdruck (311 kbar). Diese eindrucksvollen Werte wurden mithilfe geeigneter experimenteller Tests verifiziert.
Plasmon‐Assisted Water Splitting Using Two Sides of the Same SrTiO3 Single‐Crystal Substrate: Conversion of Visible Light to Chemical Energy
Authors: Zhong Yuqing , Ueno Kosei , Mori Yuko , Shi Xu , Oshikiri Tomoya , Murakoshi Kei , Inoue Haruo , Misawa Hiroaki
Published: July 2014

A plasmon‐induced water splitting system that operates under irradiation by visible light was successfully developed; the system is based on the use of both sides of the same strontium titanate (SrTiO3) single‐crystal substrate. The water splitting system contains two solution chambers to separate hydrogen (H2) and oxygen (O2). To promote water splitting, a chemical bias was applied by regulating the pH values of the chambers. The quantity of H2 evolved from the surface of platinum, which was used as a reduction co‐catalyst, was twice the quantity of O2 evolved from an Au‐nanostructured surface. Thus, the stoichiometric evolution of H2 and O2 was clearly demonstrated. The hydrogen‐evolution action spectrum closely corresponds to the plasmon resonance spectrum, indicating that the plasmon‐induced charge separation at the Au/SrTiO3 interface promotes water oxidation and the subsequent reduction of a proton on the backside of the SrTiO3 substrate. The chemical bias is significantly reduced by plasmonic effects, which indicates the possibility of constructing an artificial photosynthesis system with low energy consumption.
Helical Packing of Nanoparticles Confined in Cylindrical Domains of a Self‐Assembled Block Copolymer Structure
Authors: Sanwaria Sunita , Horechyy Andriy , Wolf Daniel , Chu Che‐Yi , Chen Hsin‐Lung , Formanek Petr , Stamm Manfred , Srivastava Rajiv , Nandan Bhanu
Published: July 2014

Theoretical models predict that a variety of self‐assembled structures of closely packed spherical particles may result when they are confined in a cylindrical domain. In the present work we demonstrate for the first time that the polymer‐coated nanoparticles confined in the self‐assembled cylindrical domains of a block copolymer pack in helical morphology, where we can isolate individual fibers filled with helically arranged nanoparticles. This finding provides unique possibilities for fundamental as well as application‐oriented research in similar directions.
From Perylene to a 22‐Ring Aromatic Hydrocarbon in One‐Pot
Authors: Schuler Bruno , Collazos Sara , Gross Leo , Meyer Gerhard , Pérez Dolores , Guitián Enrique , Peña Diego
Published: July 2014

The successful synthesis of a threefold symmetric C78H36 molecule with 22 fused benzene rings is reported. This clover‐shaped nanographene was characterized on an ultrathin insulating film with atomic resolution by scanning probe microscopy.
The CH Activation/1,3‐Diyne Strategy: Highly Selective Direct Synthesis of Diverse Bisheterocycles by RhIII Catalysis
Authors: Yu Da‐Gang , de Azambuja Francisco , Gensch Tobias , Daniliuc Constantin G. , Glorius Frank
Published: July 2014

The reactivity and selectivity of 1,3‐diynes in transition‐metal‐catalyzed CH activation is exploited to quickly assemble diverse polysubstituted bisheterocycles, which are highly important but difficult to access. By using the CH activation/1,3‐diyne strategy, we overcame the challenges of selectivity (chemo‐, regio‐, and mono‐/diannulation) and constructed seven kinds of adjacent bisheterocycles through the formation of four strategic bonds with high efficiency and high selectivity.
Accessing Zinc Monohydride Cations through Coordinative Interactions
Authors: Lummis Paul A. , Momeni Mohammad R. , Lui Melanie W. , McDonald Robert , Ferguson Michael J. , Miskolzie Mark , Brown Alex , Rivard Eric
Published: July 2014

We present isolable examples of formal zinc hydride cations supported by N‐heterocyclic carbene (NHC) donors, and investigate the dual electrophilic and nucleophilic (hydridic) character of the encapsulated [ZnH]+ units by computational methods and preliminary hydrosilylation catalysis.
Trinuclear Gold Clusters Supported by Cyclic (alkyl)(amino)carbene Ligands: Mimics for Gold Heterogeneous Catalysts
Authors: Jin Liqun , Weinberger David S. , Melaimi Mohand , Moore Curtis E. , Rheingold Arnold L. , Bertrand Guy
Published: July 2014

The synthesis of air‐ and moisture‐stable trinuclear mixed‐valence gold(I)/gold(0) clusters is described. They promote the catalytic carbonylation of amines under relatively mild conditions. The synthetic route leading to the trinuclear clusters involves a simple ligand exchange from the readily available μ3‐oxo‐[(Ph3PAu)3O]+ complex. This synthetic method paves the way for the preparation of a variety of mixed‐valence gold(I)/gold(0) polynuclear clusters. Moreover, the well‐defined nature of the complexes demonstrates that the catalytic process involves a rare example of a definite change of oxidation state of gold from Au02AuI to AuI3.
Alcohol oxidation reactions catalyzed by ruthenium–carbonyl complexes of thioarylazoimidazoles
Authors: Sarkar Shyamal Kumar , Jana Mahendra Sekhar , Mondal Tapan Kumar , Sinha Chittaranjan
Published: July 2014

Alcohols are oxidized byN‐methylmorpholine‐N‐oxide (NMO), ButOOH and H2O2to the corresponding aldehydes or ketones in the presence of catalyst, [RuH(CO)(PPh3)2(SRaaiNR′)]PF6(2) and [RuCl(CO)(PPh3)(SκRaaiNR′)]PF6(3) (SRaaiNR′ (1) = 1‐alkyl‐2‐{(o‐thioalkyl)phenylazo}imidazole, a bidentate N(imidazolyl) (N), N(azo) (N′) chelator and SκRaaiNR′ is a tridentate N(imidazolyl) (N), N(azo) (N′), Sκ‐R is tridentate chelator; R and R′ are Me and Et). The single‐crystal X‐ray structures of [RuH(CO)(PPh3)2(SMeaaiNMe)]PF6(2a) (SMeaaiNMe = 1‐methyl‐2‐{(o‐thioethyl)phenylazo}imidazole) and [RuH(CO)(PPh3)2(SEtaaiNEt)]PF6(2b) (SEtaaiNEt = 1‐ethyl‐2‐{(o‐thioethyl)phenylazo}imidazole) show bidentate N,N′ chelation, while in [RuCl(CO)(PPh3)(SκEtaaiNEt)]PF6(3b) the ligand SκEtaaiNEt serves as tridentate N,N′,S chelator. The cyclic voltammogram shows RuIII/RuII(~1.1 V) and RuIV/RuIII(~1.7 V) couples of the complexes 2 while RuIII/RuII(1.26 V) couple is observed only in3along with azo reductions in the potential window +2.0 to −2.0 V. DFT computation has been used to explain the spectra and redox properties of the complexes. In the oxidation reaction NMO acts as best oxidant and [RuCl(CO)(PPh3)(SκRaaiNR′)](PF6) (3) is the best catalyst. The formation of high‐valent RuIV=O species as a catalytic intermediate is proposed for the oxidation process. Copyright © 2014 John Wiley & Sons, Ltd.
Ligand‐free Pd/Cu‐catalyzed decarboxylative coupling of aryl iodides with α‐oxocarboxylates
Authors: Ji Yongfeng , Yang Xiaomin , Mao Weixi
Published: July 2014

This paper describes a palladium/copper‐catalyzed decarboxylative coupling of aryl iodides with α‐oxocarboxylates. The cross‐coupling reaction gives high chemical yields of aryl ketones and has wide functional group tolerance, making the transformation an attractive alternative to the traditional cross‐coupling approaches for aryl ketones. Copyright © 2014 John Wiley & Sons, Ltd.
Development of a pressure–volume–temperature measurement method for thermoplastic materials based on compression injection molding
Authors: Szabó Ferenc , Kovács József G.
Published: July 2014

The pressure–volume–temperature (pvT) relationship of polymers is vitally important information in designing and manufacturing polymers. Because of the special behavior of polymers, however, it is extremely difficult to accurately measure the data in a way that matches the thermal conditions of injection molding, which is one of the most widely used processing methods. As neither widely used, commercially available measuring devices, nor special equipment mentioned in the literature can fully satisfy this need, it was decided to build a new device able to determine the pvT relationship during injection molding of the polymer. The new device consists of a special mold that can be used on an injection molding machine and a data collection system connected to it. With the help of this device, pvT data can be measured during processing according to the thermal conditions of injection molding, and also considerably faster, and even in an industrial setting. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41140.
De Novo Synthesis of Imidazoles by Visible‐Light‐Induced Photocatalytic Aerobic Oxidation/[3+2] Cycloaddition/Aromatization Cascade
Authors: Deng Qiao‐Hui , Zou You‐Quan , Lu Liang‐Qiu , Tang Zi‐Long , Chen Jia‐Rong , Xiao Wen‐Jing
Published: July 2014

A visible‐light‐induced photocatalytic aerobic oxidation/[3+2] cycloaddition/aromatization cascade between secondary amines and isocyanides has been successfully developed. The reaction provides a general and efficient access to diversely substituted imidazoles and imidazo[1,5‐a]quinoxalin‐4(5 H)‐ones in good yields under mild conditions.
Anthropogenic CO2 as a feedstock for the production of algal‐based biofuels
Authors: Lively Ryan P. , Sharma Pradeep , McCool Benjamin A. , Beaudry‐Losique Jacques , Luo Dexin , Thomas Valerie M. , Realff Matthew , Chance Ronald R.
Published: July 2014

Biofuels have great potential as low‐carbon transportation fuel alternatives and can be essentially drop‐in fuels for existing fossil‐fuel‐based transportation infrastructures. Thus, the incentives for biofuel development are large but there are a number of issues: competition with food, land use, fresh water use, economics in comparison to fossil fuels, and achievable reduction in carbon footprint in comparison to other transportation fuel options. This paper focuses on utilization of anthropogenic CO2 from power plants in advanced biofuel production systems and the integration of those systems with various power plant designs. In doing so, the boundary of the life cycle analysis is expanded to include the power plant CO2 source, considering specifically natural gas, pulverized coal, supercritical coal, and IGCC (integrated gasification combined cycle) options. The carbon footprints for the integrated systems are compared to CCS (carbon capture and sequestration) as well as the current status quo of CO2 release to the atmosphere. The integrated biorefinery‐power plant options considered here are shown to be greatly advantaged compared to the status quo (no CO2 capture) carbon footprint, and also advantaged with respect to CCS as long as the biorefinery alone operates with a carbon footprint that is 75% or more lower than that of gasoline. In addition, the projected carbon footprint values, and estimated production costs, for algal‐based ethanol are favorable compared to other transportation fuel options including corn‐based ethanol and electricity. © 2014 Society of Chemical Industry and John Wiley & Sons, Ltd
Advice from Experience: Communicating Incomplete Information Incompletely
Authors: Benjamin Daniel , Budescu David V.
Published: July 2014

People utilize advice often with limited knowledge of their advisers' expertise. We examine the effects of learning mode on giving and receiving advice in two separate but linked studies. Advisers learned about a choice between two lotteries from either description or experience before writing advice. The decision makers only read this advice before choosing between the options. Advisers who learned from description provided better summarized information more confidently and were ultimately preferred by the decision makers. Advisers who learned from experience were more risk averse and tended to describe their experiences signaling their informational deficiency. Decision makers were sensitive to the subtle differences between the two cases, even when not informed of their adviser's learning mode. We discuss the implications of the adviser's learning mode within the context of various decision environments and the risk‐uncertainty continuum. Advisers perform under risk when learning from description compared with performing under uncertainty when learning from experience. Copyright © 2014 John Wiley & Sons, Ltd.
Elektrochemische Potentialmessungen zum Auffinden von Bewehrungskorrosion
Authors: Mayer Till Felix
Published: July 2014

Seit Erscheinen der ersten Ausgabe des Merkblatts B3 der DGZfP im Jahre 1990 hat sich die Potentialfeldmessung als Standardverfahren zum Auffinden von Bewehrungskorrosion im Rahmen von Zustandserfassungen und Instandsetzungsplanungen etabliert. Im Jahr 2014 erscheint eine überarbeitete Fassung des Merkblatts, die sich zum Ziel gesetzt hat, durch Konkretisierung der Anforderungen an die Qualifikation des Prüfpersonals, die Ausschreibung, Durchführung und Interpretation der Messungen eine Vergleichmäßigung der Qualität durchgeführter Potentialfeldmessungen zu erreichen. Wesentliche Neuerungen gegenüber früheren Fassungen des Merkblatts werden im Folgenden kurz dargestellt.

Electrochemical half‐cell potential measurements for the detection of reinforcement corrosion – New version of the bulletin B3 of the German Society for Non‐destructive Testing DGZfP

Since the publication of the first version of the bulletin in 1990 half‐cell potential measurement has been established as a standard test method to detect reinforcement corrosion. In 2014 a new version of the bulletin will be published. Some of the main differences with respect to the former versions will briefly be presented in this paper.
Comparison of genome‐wide selection strategies to identify furfural tolerance genes in Escherichia coli
Authors: Glebes Tirzah Y. , Sandoval Nicholas R. , Gillis Jacob H. , Gill Ryan T.
Published: July 2014

Engineering both feedstock and product tolerance is important for transitioning towards next‐generation biofuels derived from renewable sources. Tolerance to chemical inhibitors typically results in complex phenotypes, for which multiple genetic changes must often be made to confer tolerance. Here, we performed a genome‐wide search for furfural‐tolerant alleles using the TRackable Multiplex Recombineering (TRMR) method (Warner et al. (2010), Nature Biotechnology), which uses chromosomally integrated mutations directed towards increased or decreased expression of virtually every gene in Escherichia coli. We employed various growth selection strategies to assess the role of selection design towards growth enrichments. We also compared genes with increased fitness from our TRMR selection to those from a previously reported genome‐wide identification study of furfural tolerance genes using a plasmid‐based genomic library approach (Glebes et al. (2014) PLOS ONE). In several cases, growth improvements were observed for the chromosomally integrated promoter/RBS mutations but not for the plasmid‐based overexpression constructs. Through this assessment, four novel tolerance genes, ahpC, yhjH, rna, and dicA, were identified and confirmed for their effect on improving growth in the presence of furfural. Biotechnol. Bioeng. 2015;112: 129–140. © 2014 Wiley Periodicals, Inc.
Molybdenum Sulfides and Selenides as Possible Electrocatalysts for CO2 Reduction
Authors: Chan Karen , Tsai Charlie , Hansen Heine A. , Nørskov Jens K.
Published: July 2014

Linear scaling relations between reaction intermediates pose a fundamental limitation to the CO2 reduction activity of transition‐metal catalysts. To design improved catalysts, we propose to break these scaling relations by binding key reaction intermediates to different sites. Using density functional theory, we demonstrate this principle in the active edge sites in MoS2, MoSe2, and Ni‐doped MoS2. These edges show the unique property of selectively binding COOH and CHO to bridging S or Se atoms and CO to the metal atom. DFT calculations suggest a significant improvement in CO2 reduction activity over the transition metals. Our results point to the broader application of the active edge sites of transition‐metal dichalcogenides in complex electrochemical processes.
High‐Performance Sodium‐Ion Batteries and Sodium‐Ion Pseudocapacitors Based on MoS2/Graphene Composites
Authors: Wang Yun‐Xiao , Chou Shu‐Lei , Wexler David , Liu Hua‐Kun , Dou Shi‐Xue
Published: July 2014

Sodium‐ion energy storage, including sodium‐ion batteries (NIBs) and electrochemical capacitive storage (NICs), is considered as a promising alternative to lithium‐ion energy storage. It is an intriguing prospect, especially for large‐scale applications, owing to its low cost and abundance. MoS2 sodiation/desodiation with Na ions is based on the conversion reaction, which is not only able to deliver higher capacity than the intercalation reaction, but can also be applied in capacitive storage owing to its typically sloping charge/discharge curves. Here, NIBs and NICs based on a graphene composite (MoS2/G) were constructed. The enlarged d‐spacing, a contribution of the graphene matrix, and the unique properties of the MoS2/G substantially optimize Na storage behavior, by accommodating large volume changes and facilitating fast ion diffusion. MoS2/G exhibits a stable capacity of approximately 350 mAh g−1 over 200 cycles at 0.25 C in half cells, and delivers a capacitance of 50 F g−1 over 2000 cycles at 1.5 C in pseudocapacitors with a wide voltage window of 0.1–2.5 V.
Stereodivergent Organocatalytic Intramolecular Michael Addition/Lactonization for the Asymmetric Synthesis of Substituted Dihydrobenzofurans and Tetrahydrofurans
Authors: Belmessieri Dorine , de la Houpliere Alix , Calder Ewen D. D. , Taylor James E. , Smith Andrew D.
Published: July 2014

A stereodivergent asymmetric Lewis base catalyzed Michael addition/lactonization of enone acids into substituted dihydrobenzofuran and tetrahydrofuran derivatives is reported. Commercially available (S)‐(−)‐tetramisole hydrochloride gives products with high syn diastereoselectivity in excellent enantioselectivity (up to 99:1 d.r.syn/anti, 99 % eesyn), whereas using a cinchona alkaloid derived catalyst gives the corresponding anti‐diastereoisomers as the major product (up to 10:90 d.r.syn/anti, 99 % eeanti).
Characterization of a Robust CoII Fluorescent Complex Deposited Intact On HOPG
Authors: Heras‐Ojea María José , Mañeru Daniel Reta , Rosado Lidia , Zuazo Juan Rubio , Castro German R. , Tewary Subrata , Rajaraman Gopalan , Aromí Guillem , Jiménez Erika , Sañudo E. Carolina
Published: July 2014

The new diimine fluorescent ligand ACRI‐1 based on a central acridine yellow core is reported along with its coordination complex [Co2(ACRI‐1)2] (1), a fluorescent weak ferromagnet. Due to the strong fluorescence of the acridine yellow fluorophore, it is not completely quenched when the ligand is coordinated to CoII. The magnetic properties of bulk complex 1 and its stability in solution have been studied. Complex 1 has been deposited on highly ordered pyrolitic graphite (HOGP) from solution. The thin films prepared have been characterized by AFM, time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS), grazing incidence X‐ray diffraction (GIXRD), X‐ray absorption spectroscopy (XAS), X‐ray magnetic circular dichroism (XMCD) and theoretical calculations. The data show that the complex is robust and remains intact on the surface of graphite.
Hybrid Mesoporous Silica Nanoparticles with pH‐Operated and Complementary H‐Bonding Caps as an Autonomous Drug‐Delivery System
Authors: Théron Christophe , Gallud Audrey , Carcel Carole , Gary‐Bobo Magali , Maynadier Marie , Garcia Marcel , Lu Jie , Tamanoi Fuyuhiko , Zink Jeffrey I. , Wong Chi Man Michel
Published: July 2014

Mesoporous silica nanoparticles (MSNPs) are functionalized with molecular‐recognition sites by anchoring a triazine or uracil fragment on the surface. After loading these MSNPs with dyes (propidium iodide or rhodamine B) or with a drug (camptothecin, CPT) they are capped by the complementary fragments, uracil and adenine, respectively, linked to the bulky cyclodextrin ring. These MSNPs are pH‐sensitive and indeed, the dye release was observed at acidic pH by continuously monitored fluorescence spectroscopy studies. On the other hand, no dye leakage occurred at neutral pH, hence meeting the non‐premature requirement to minimize side effects. In vitro studies were performed and confocal microscopy images demonstrate the internalization of the MSNPs and also dye release in the cells. To investigate the drug‐delivery performance, the cytotoxicity of CPT‐loaded nanoparticles was tested and cell death was observed. A remarkably lower amount of loaded CPT in the MSNPs (more than 40 times less) proved to be as efficient as free CPT. These results not only demonstrate the drug release after pore opening under lysosomal pH, but they also show the potential use of these MSNPs to significantly decrease the amount of the administered drug.
Cesium Carbonate Catalyzed Chemoselective Hydrosilylation of Aldehydes and Ketones under Solvent‐Free Conditions
Authors: Zhao Mengdi , Xie Weilong , Cui Chunming
Published: July 2014

Cs2CO3 has been found to be an efficient and chemoselective catalyst for reduction of aldehydes and ketones to alcohols with one equivalent of Ph2SiH2 as the reductant under solvent‐free conditions. Most of the aldehydes employed can be effectively hydrosilated quantitatively to give the corresponding silyl ethers in 2 h at room temperature, whereas the hydrosilylation of ketones proceeded smoothly at 80 °C. The catalyst system tolerates a number of functional groups including halogen, alkoxyl, olefin, ester, nitro, cyano, and heteroaromatic groups; the selective hydrosilylation of aldehydes in the presence of ketone can be effectively controlled by temperature; and hydrosilylation of α,β‐unsaturated carbonyls resulted in the 1,2‐addition products. The catalytic hydrosilylation of suitable dicarbonyls can be applied to the synthesis of poly(silyl ether)s with a high molecular weight and narrow molecular distribution.
Combinatorial Multicomponent Access to Natural‐Products‐Inspired Peptidomimetics: Discovery of Selective Inhibitors of Microbial Metallo‐aminopeptidases
Authors: Méndez Yanira , Pérez‐Labrada Karell , González‐Bacerio Jorge , Valdés Gilberto , de los Chávez María Á. , Osuna Joel , Charli Jean‐Louis , Pascual Isel , Rivera Daniel G.
Published: July 2014

The development of selective inhibitors of microbial metallo‐aminopeptidases is an important goal in the pursuit of antimicrobials for therapeutic applications. Herein, we disclose a combinatorial approach relying on two Ugi reactions for the generation of peptidomimetics inspired by natural metallo‐aminopeptidase inhibitors. The library was screened for inhibitory activity against the neutral metallo‐aminopeptidase of Escherichia coli (ePepN) and the porcine kidney cortex metallo‐aminopeptidase (pAPN), which was used as a model of the M1‐aminopeptidases of mammals. Six compounds showed typical dose–response inhibition profiles toward recombinant ePepN, with two of them being very potent and highly selective for ePepN over pAPN. Another compound showed moderate ePepN inhibition but total selectivity for this bacterial enzyme over its mammalian orthologue at concentrations of physiological relevance. This strategy proved to be useful for the identification of lead compounds for further optimization and development.