bluuebunny/crossref_metadata_2025 huggingface dataset:
Chemical imaging of ambient aerosol particles: Observational constraints on mixing state parameterization
Authors: O'Brien Rachel E. , Wang Bingbing , Laskin Alexander , Riemer Nicole , West Matthew , Zhang Qi , Sun Yele , Yu Xiao‐Ying , Alpert Peter , Knopf Daniel A. , Gilles Mary K. , Moffet Ryan C.
Published: August 2015

A new parameterization for quantifying the mixing state of aerosol populations has been applied for the first time to samples of ambient particles analyzed using spectro‐microscopy techniques. Scanning transmission X‐ray microscopy/near edge X‐ray absorption fine structure (STXM/NEXAFS) and computer‐controlled scanning electron microscopy/energy dispersive X‐ray spectroscopy (CCSEM/EDX) were used to probe the composition of the organic and inorganic fraction of individual particles collected on 27 and 28 June during the 2010 Carbonaceous Aerosols and Radiative Effects study in the Central Valley, California. The first field site, T0, was located in downtown Sacramento, while T1 was located near the Sierra Nevada Mountains. Mass estimates of the aerosol particle components were used to calculate mixing state metrics, such as the particle‐specific diversity, bulk population diversity, and mixing state index, for each sample. The STXM data showed evidence of changes in the mixing state associated with a buildup of organic matter confirmed by collocated measurements, and the largest impact on the mixing state was due to an increase in soot dominant particles during this buildup. The mixing state from STXM was similar between T0 and T1, indicating that the increased organic fraction at T1 had a small effect on the mixing state of the population. The CCSEM/EDX analysis showed the presence of two types of particle populations: the first was dominated by aged sea‐salt particles and had a higher mixing state index (indicating a more homogeneous population); the second was dominated by carbonaceous particles and had a lower mixing state index.
Evaluation of tropical channel refinement using MPAS‐A aquaplanet simulations
Authors: Martini Matus N. , Gustafson William I. , O'Brien Travis A. , Ma Po‐Lun
Published: August 2015

Climate models with variable‐resolution grids offer a computationally less expensive way to provide more detailed information and increased accuracy by resolving processes that cannot be adequately represented by a coarser grid. This study uses the Model for Prediction Across Scales‐Atmosphere (MPAS‐A), consisting of a nonhydrostatic dynamical core and a subset of Weather Research and Forecasting (WRF) model physics, to investigate the potential benefits of using tropical channel refinement. The simulations are performed with an idealized aquaplanet configuration using 30 and 240 km global grid spacing, and two variable‐resolution grids spanning the same grid spacing range; one with a narrow (20°S–20°N) and one with a wide (30°S–30°N) tropical channel refinement. Increasing resolution in the tropics impacts both the tropical and extratropical circulation. Compared to the 30 km global grid, both refined channel simulations exhibit slightly stronger updrafts inside the Hadley cell resulting in more resolved precipitation. Using a wider tropical refinement leads to a closer correspondence with the global high‐resolution grid. While different grid spacings produce similar cloud size distributions that are consistent with observations, the dependence of precipitation rate on cloud size varies among simulations. The refined channel simulations show improved tropical and extratropical precipitation relative to the global coarse simulation. All simulations show a single precipitation peak centered on the equator. Although the results show that tropical refinement is an effective method for avoiding artifacts due to grid resolution sensitivities seen in earlier studies that only refined a portion of the tropics, some biases remain well inside of the refinement region.
Adaptive filters cascade applied to a frequency identification improvement problem
Authors: Aranovskiy Stanislav V. , Bobtsov Alexey A. , Pyrkin Anton A. , Gritcenko Polina A.
Published: August 2015

Problem of frequency identification performance improvement for a single‐tone sinusoidal signal is solved via construction of an adaptive filters cascade. The cascade consists of adaptive band‐pass filters tuned by estimates of the frequency provided by a given identification algorithm. Stability of the cascade is studied and boundedness of trajectories is proven with Lyapunov analysis under certain assumption on identification algorithm. Numerical simulations are given illustrating improved identification performance for different identification algorithms. Copyright © 2015 John Wiley & Sons, Ltd.
High Throughput Discovery of Solar Fuels Photoanodes in the CuO–V2O5 System
Authors: Zhou Lan , Yan Qimin , Shinde Aniketa , Guevarra Dan , Newhouse Paul F. , Becerra‐Stasiewicz Natalie , Chatman Shawn M. , Haber Joel A. , Neaton Jeffrey B. , Gregoire John M.
Published: August 2015

Solar photoelectrochemical generation of fuel is a promising energy technology yet the lack of an efficient, robust photoanode remains a primary materials challenge in the development and deployment of solar fuels generators. Metal oxides comprise the most promising class of photoanode materials, but no known material meets the demanding requirements of low band gap energy, photoelectrocatalysis of the oxygen evolution reaction (OER), and stability under highly oxidizing conditions. Here, the identification of new photoelectroactive materials is reported through a strategic combination of combinatorial materials synthesis, high‐throughput photoelectrochemistry, optical spectroscopy, and detailed electronic structure calculations. Four photoelectrocatalyst phases, α‐Cu2V2O7, β‐Cu2V2O7,γ‐Cu3V2O8, and Cu11V6O26, are reported with band gap energy at or below 2 eV. The photoelectrochemical properties and 30 min stability of these copper vanadate phases are demonstrated in three different aqueous electrolytes (pH 7, pH 9, and pH 13), with select combinations of phase and electrolyte exhibiting unprecedented photoelectrocatalytic stability for metal oxides with sub‐2 eV band gap. Through integration of experimental and theoretical techniques, new structure‐property relationships are determined and establish CuO–V2O5 as the most prominent composition system for OER photoelectrocatalysts, providing crucial information for materials genomes initiatives and paving the way for continued development of solar fuels photoanodes.
Site‐Directed, On‐Surface Assembly of DNA Nanostructures
Authors: Meyer Rebecca , Saccà Barbara , Niemeyer Christof M.
Published: August 2015

Two‐dimensional DNA lattices have been assembled from DNA double‐crossover (DX) motifs on DNA‐encoded surfaces in a site‐specific manner. The lattices contained two types of single‐stranded protruding arms pointing into opposite directions of the plane. One type of these protruding arms served to anchor the DNA lattice on the solid support through specific hybridization with surface‐bound, complementary capture oligomers. The other type of arms allowed for further attachment of DNA‐tethered probe molecules on the opposite side of the lattices exposed to the solution. Site‐specific lattice assembly and attachment of fluorophore‐labeled oligonucleotides and DNA–protein conjugates was demonstrated using DNA microarrays on flat, transparent mica substrates. Owing to their programmable orientation and addressability over a broad dynamic range from the nanometer to the millimeter length scale, such supramolecular architecture might be used for presenting biomolecules on surfaces, for instance, in biosensor applications.
Large‐Area, Free‐Standing, Two‐Dimensional Supramolecular Polymer Single‐Layer Sheets for Highly Efficient Electrocatalytic Hydrogen Evolution
Authors: Dong Renhao , Pfeffermann Martin , Liang Haiwei , Zheng Zhikun , Zhu Xiang , Zhang Jian , Feng Xinliang
Published: August 2015

The rational construction of covalent or noncovalent organic two‐dimensional nanosheets is a fascinating target because of their promising applications in electronics, membrane technology, catalysis, sensing, and energy technologies. Herein, a large‐area (square millimeters) and free‐standing 2D supramolecular polymer (2DSP) single‐layer sheet (0.7–0.9 nm in thickness), comprising triphenylene‐fused nickel bis(dithiolene) complexes has been readily prepared by using the Langmuir–Blodgett method. Such 2DSPs exhibit excellent electrocatalytic activities for hydrogen generation from water with a Tafel slope of 80.5 mV decade−1 and an overpotential of 333 mV at 10 mA cm−2, which are superior to that of recently reported carbon nanotube supported molecular catalysts and heteroatom‐doped graphene catalysts. This work is promising for the development of novel free‐standing organic 2D materials for energy technologies.
Multidimensional Electronic Spectroscopy of Photochemical Reactions
Authors: Nuernberger Patrick , Ruetzel Stefan , Brixner Tobias
Published: August 2015

Coherent multidimensional electronic spectroscopy can be employed to unravel various channels in molecular chemical reactions. This approach is thus not limited to analysis of energy transfer or charge transfer (i.e. processes from photophysics), but can also be employed in situations where the investigated system undergoes permanent structural changes (i.e. in photochemistry). Photochemical model reactions are discussed by using the example of merocyanine/spiropyran‐based molecular switches, which show a rich variety of reaction channels, in particular ring opening and ring closing, cis–trans isomerization, coherent vibrational wave‐packet motion, radical ion formation, and population relaxation. Using pump‐probe, pump‐repump‐probe, coherent two‐dimensional and three‐dimensional, triggered‐exchange 2D, and quantum‐control spectroscopy, we gain intuitive pictures on which product emerges from which reactant and which reactive molecular modes are associated.
Ortho‐Stabilized 18F‐Azido Click Agents and their Application in PET Imaging with Single‐Stranded DNA Aptamers
Authors: Wang Lu , Jacobson Orit , Avdic Din , Rotstein Benjamin H. , Weiss Ido D. , Collier Lee , Chen Xiaoyuan , Vasdev Neil , Liang Steven H.
Published: August 2015

Azido 18F‐arenes are important and versatile building blocks for the radiolabeling of biomolecules via Huisgen cycloaddition (“click chemistry”) for positron emission tomography (PET). However, routine access to such clickable agents is challenged by inefficient and/or poorly defined multistep radiochemical approaches. A high‐yielding direct radiofluorination for azido 18F‐arenes was achieved through the development of an ortho‐oxygen‐stabilized iodonium derivative (OID). This OID strategy addresses an unmet need for a reliable azido 18F‐arene clickable agent for bioconjugation reactions. A ssDNA aptamer was radiolabeled with this agent and visualized in a xenograft mouse model of human colon cancer by PET, which demonstrates that this OID approach is a convenient and highly efficient way of labeling and tracking biomolecules.
Gender as an influencer of online health information‐seeking and evaluation behavior
Authors: Rowley Jennifer , Johnson Frances , Sbaffi Laura
Published: August 2015

This article contributes to the growing body of research that explores the significance of context in health information behavior. Specifically, through the lens of trust judgments, it demonstrates that gender is a determinant of the information evaluation process. A questionnaire‐based survey collected data from adults regarding the factors that influence their judgment of the trustworthiness of online health information. Both men and women identified credibility, recommendation, ease of use, and brand as being of importance in their trust judgments. However, women also take into account style, while men eschew this for familiarity. In addition, men appear to be more concerned with the comprehensiveness and accuracy of the information, the ease with which they can access it, and its familiarity, whereas women demonstrate greater interest in cognition, such as the ease with which they can read and understand the information. These gender differences are consistent with the demographic data, which suggest that: women consult more types of sources than men; men are more likely to be searching with respect to a long‐standing health complaint; and, women are more likely than men to use tablets in their health information seeking. Recommendations for further research to better inform practice are offered.
Mechanism of Nickel(II)‐Catalyzed Oxidative C(sp2)−H/C(sp3)−H Coupling of Benzamides and Toluene Derivatives
Authors: Xu Zheng‐Yang , Jiang Yuan‐Ye , Yu Hai‐Zhu , Fu Yao
Published: August 2015

The Ni‐catalyzed C(sp2)−H/C(sp3)−H coupling of benzamides with toluene derivatives was recently successfully achieved with mild oxidant iC3F7I. Herein, we employ density functional theory (DFT) methods to resolve the mechanistic controversies. Two previously proposed mechanisms are excluded, and our proposed mechanism involving iodine‐atom transfer (IAT) between iC3F7I and the NiII intermediate was found to be more feasible. With this mechanism, the presence of a carbon radical is consistent with the experimental observation that (2,2,6,6‐tetramethylpiperidin‐1‐yl)oxyl (TEMPO) completely quenches the reaction. Meanwhile, the hydrogen‐atom abstraction of toluene is irreversible and the activation of the C(sp2)−H bond of benzamides is reversible. Both of these conclusions are in good agreement with Chatani's deuterium‐labeling experiments.
Isoguaiacins, Arylnaphthalene Types Identified as Novel Potent Estrogenic Signaling Molecules from Larrea nitida
Authors: Jeong Si‐Yeon , Ahn Hye‐na , Bae Gyu‐Un , Chang Minsun , Liu Xiyuan , Rhee Hee‐Kyung , Lee Joongku , Chin Young‐Won , Oh Sei‐Ryang , Song Yun Seon
Published: August 2015

In our study on the biological activities of isoguaiacins, we demonstrated lignans with a rigid structure from Larrea nitida as selective estrogen receptor modulators (SERMs). Estrogenic activity‐guided isolation of the L. nitida extract led to the identification of four lignans compounds. All four lignans displayed high binding affinity for human estrogen receptor (hER) α and β as well as transcriptional activities for estrogen response element (ERE). Furthermore, arylnaphthalene type lignans 1 (5,6,7,8‐tetrahydro‐5‐(3,4‐dihydroxyphenyl)‐6,7‐dimethylnaphthalene‐2,3‐diol) and 2 (5,6,7,8‐tetrahydro‐5‐(4‐hydroxy‐3‐methoxyphenyl)‐6,7‐dimethylnaphthalene‐2,3‐diol) showed especially high potencies for ERβ and ERE with IC50
of 0.045 and 0.85 μM, respectively. Arylnaphthalene type lignans 1 and 2 and bibenzyl butane type lignans 3 (4‐(4‐(4‐hydroxyphenyl)‐2,3‐dimethylbutyl) benzene‐1,2‐diol) increased the proliferation of MCF‐7 cells and the ERα target gene
pS2
. Our results indicate that the four active lignans have selective affinities for hERβ and exhibit SERM properties. For the first time, we have discovered the estrogenic activities of isoguaiacins from L. nitida, which are promising candidates for the treatment of estrogen‐related conditions and warrant further preclinical evaluation.
Transient neonatal diabetes due to a missense mutation (E227K) in the gene encoding the ATP‐sensitive potassium channel (KCNJ11)
Authors: Martins Luísa , Lourenço Rita , Maia Ana Lúcia , Maciel Paula , Monteiro Maria Isabel , Pacheco Lucinda , Anselmo João , César Rui , Gomes Maria Fernanda
Published: August 2015

Key Clinical Message

Neonatal diabetes is a monogenic form of diabetes. Herein, we report on a newborn presenting diabetic ketoacidosis at 17 days of life . A KCNJ11 mutation was identified. In such cases, insulin can be replaced by sulfonylurea with a successful metabolic control, as an example of how molecular diagnosis may influence the clinical management of the disorder.
Are de novo rea(21;21) chromosomes really de novo?
Authors: Hervé Bérénice , Quibel Thibaud , Taieb Stéphane , Ruiz Mireille , Molina‐Gomes Denise , Vialard François
Published: August 2015

Key Clinical Message

We report a rare case of recurrent trisomy 21 caused by an isochromosome 21q and what is very likely to be maternal germ‐line cell mosaicism. Over 90% of cases of rob(21;21) reported in the literature are due to an isochromosome 21q, with a risk of recurrence of more than 10%.
Early‐onset hypoparathyroidism and chronic keratitis revealing APECED
Authors: Mezgueldi Ellia , Bertholet‐Thomas Aurélia , Milazzo Solange , Morris Michael , Bacchetta Justine , Fabien Nicole , Cochat Pierre , Weetman Anthony P. , Kemp Elizabeth Helen , Belot Alexandre
Published: August 2015

Key Clinical Message

Early diagnosis of potentially life‐threatening autoimmune polyendocrinopathy‐candidiasis‐ectodermal dystrophy (APECED) is crucial, but is often delayed due to the clinical heterogeneity of the disorder. Even in the absence of the classic disease triad of chronic mucocutaneous candidiasis, hypoparathyroidism, and adrenocortical insufficiency, a diagnosis of APECED should be considered in children who have hypoparathyroidism and chronic keratitis, with a past medical history showing a mild and transient Candida infection.
Kinetic Model for Invertase‐Induced Sucrose Hydrolysis: Initial Time Lag
Authors: Keramat Ali , Kargari Ali , Sohrabi† Morteza , Mirshekar Hamed , Sanaeepur Hamidreza
Published: August 2015

The kinetics of sucrose hydrolysis by invertase was studied in order to find a comprehensive model for the reaction pathway and mechanism. First, three common models of Michaelis‐Menten (MM), substrate inhibition (S2), and substrate clusters' inhibition (S3(I)) were investigated. The third model was found to better predict the initial sucrose concentration. Then, the S3(I) model was modified to cover the remaining pathway (S3(II)). Finally, a new comprehensive model (S3(III)) was evaluated, which in addition to what is considered in the two previously mentioned models (S3(I) and S3(II)) also involved the initial time lag. The model predictions showed an excellent agreement with the experimental data. The mean absolute error for the MM model is significantly reduced for the S3(III) model.
Enhanced Silica Removal by Polyamine‐ and Polyacrylamide‐Polyaluminum Hybrid Coagulants
Authors: Miranda Ruben , Latour Isabel , Hörsken Arne , Jarabo Rocío , Blanco Angeles
Published: August 2015

Silica removal is the main bottleneck for a high reuse of deinking paper mill effluents due to silica scaling on the reverse‐osmosis units generally used. The efficiency of inorganic‐organic hybrid coagulants formed by the combination of polyaluminum nitrate sulfate (PANS) with different dosages of cationic polyacrylamide (PAM) or polyamines (PA) on silica removal is analyzed. These hybrids significantly increased the silica and chemical oxygen demand (COD) removal at all pH values studied, with PA modification being the most efficient. While conventional aluminum coagulants allow high silica removal, only at both high pH and dosages the PA derivatives achieve high silica and soluble COD removal without pH adjustment. PAM hybrids only slightly improved the efficiency of PANS at the highest active contents.
Retention of Biopolymers by Ultrafiltration Membranes
Authors: Arkhangelsky Elizabeth , Levitsky Inna , Gitis Vitaly
Published: August 2015

Separation of biopolymers is one of increasingly important applications of ultrafiltration (UF) membranes. The efficiency of separation is often evaluated through pilot experiments and seldom predicted. Available predictions focus on correlations between UF pore width and biopolymer hydrodynamic diameter, while overlooking key operational parameters including transmembrane pressure (TMP). The role of TMP in the retention of biopolymers is revealed, i.e., magnification of TMP leads to decreased retention of the particulates. No full retention of the biopolymers without a rigid outer shell has been observed. Pressure‐induced stretching of flexible biopolymers and expansion of membrane pores are the possible reasons of deteriorating selectivity. A division into flexible and rigid biopolymers provides a better prediction of membrane selectivity.
Electrochemistry of Nitrated N‐Confused Free‐Base Tetraaryl‐Porphyrins in Nonaqueous Media
Authors: Ye Lina , Ou Zhongping , Fang Yuanyuan , Xue Songlin , Chen Xueyan , Lu Guifen , Jiang Xiaoqin , Kadish Karl M.
Published: August 2015

Four nitrated N‐confused free‐base tetraarylporphyrins were synthesized and characterized by electrochemistry and spectroelectrochemistry in nonaqueous media. The examined compounds are represented as NO2(Ar)4NcpH2, where NO2(Ar)4Ncp is the dianion of a tetraaryl N‐confused porphyrin with an inner carbon bound NO2 group and Ar is a p‐CH3OPh, p‐CH3Ph, Ph or p‐ClPh substituent on each meso‐position of the macrocycle. UV/Vis spectra and NMR spectroscopy data indicate that the same form of the porphyrin exists in CH2Cl2 and DMF which is unlike the case of non‐NO2 N‐confused porphyrins. The Soret band of NO2(Ar)4NcpH2 exhibits a 30–36 nm red‐shift in CH2Cl2 and DMF as compared to the spectrum of the non‐NO2 N‐confused porphyrins. The first two reductions and first oxidation of NO2(Ar)4NcpH2 are reversible in CH2Cl2 containing 0.1 M TBAP. The measured HOMO–LUMO gap averages 1.65 V in CH2Cl2 and 1.53 V in DMF, with both values being similar to those of the non‐NO2 substituted compounds. The nitro group on the inverted pyrrole is itself not reduced within the negative potential limit of CH2Cl2 or DMF, but its presence significantly affects both the UV/Vis spectra and redox potentials.
New Stable and Persistent Acyclic Diaminocarbenes
Authors: Schulz Tim , Weismann Daniel , Wallbaum Lars , Guthardt Robin , Thie Charlotte , Leibold Michael , Bruhn Clemens , Siemeling Ulrich
Published: August 2015

The portfolio of acyclic diaminocarbenes (ADACs) has been substantially expanded, owing to the synthesis of eleven new formamidinium salts, mostly of the type [(iPr2N)CH(NRR′)][PF6], for use as immediate carbene precursors. The corresponding ADACs (iPr2N)C(NRR′) were sufficiently stable for isolation in the case of NRR′=2‐methylpiperidino (13), 3‐methylpiperidino (14), 4‐methylpiperidino (15), morpholino (17) and NiPrPh (20), but had to be trapped in situ in the case of NRR′=2,2,6,6‐tetramethylpiperidino (12) and NiPrMe (19). The tetraaryl‐substituted ADACs (Ph2N)2C (22) and (Ph2N)C[N(C6F5)2] (24) also could only be generated and trapped in situ. Trapping with elemental selenium was particularly efficient, affording the corresponding selenourea derivative in all cases, whereas trapping with [{Rh(μ‐Cl)(cod)}2] did not work for 12 and 24. The 77Se NMR chemical shifts, δ(77Se), of the selenourea compounds derived from the new ADACs lie in the range 450–760 ppm, which indicates a much higher electrophilicity and π‐accepting capability of ADACs in comparison with NHCs, which typically exhibit δ(77Se)<200 ppm. The extreme low‐field shift of 758 ppm observed for 12Se can be rationalised by the results of DFT calculations, which revealed that ADAC 12 has a minimum energy conformation with the 2,2,6,6‐tetramethylpiperidino unit perpendicular to the N2C plane, which suppresses the π donation of this amino group and causes an unusually low LUMO energy and high electrophilicity.
Pentacoordinated Carboxylate π‐Allyl Nickel Complexes as Key Intermediates for the Ni‐Catalyzed Direct Amination of Allylic Alcohols
Authors: Kita Yusuke , Sakaguchi Hironobu , Hoshimoto Yoichi , Nakauchi Daisuke , Nakahara Yasuhito , Carpentier Jean‐François , Ogoshi Sensuke , Mashima Kazushi
Published: August 2015

Direct amination of allylic alcohols with primary and secondary amines catalyzed by a system made of [Ni(1,5‐cyclooctadiene)2] and 1,1′‐bis(diphenylphosphino)ferrocene was effectively enhanced by adding nBu4NOAc and molecular sieves, affording the corresponding allyl amines in high yield with high monoallylation selectivity for primary amines and high regioselectivity for monosubstituted allylic alcohols. Such remarkable additive effects of nBu4NOAc were elucidated by isolating and characterizing some nickel complexes, manifesting the key role of a charge neutral pentacoordinated η3‐allyl acetate complex in the present system, in contrast to usual cationic tetracoordinated complexes earlier reported in allylic substitution reactions.
Stabilization of Titanium Dioxide Nanoparticles at the Surface of Carbon Nanomaterials Promoted by Microwave Heating
Authors: Zhang Rui , Santangelo Saveria , Fazio Enza , Neri Fortunato , D'Arienzo Massimiliano , Morazzoni Franca , Zhang Yihe , Pinna Nicola , Russo Patrícia A.
Published: August 2015

TiO2 is frequently combined with carbon materials, such as reduced graphene oxide (RGO), to produce composites with improved properties, for example for photocatalytic applications. It is shown that heating conditions significantly affect the interface and photocatalytic properties of TiO2@C, and that microwave irradiation can be advantageous for the synthesis of carbon‐based materials. Composites of TiO2 with RGO or amorphous carbon were prepared from reaction of titanium isopropoxide with benzyl alcohol. During the synthesis of the TiO2 nanoparticles, the carbon is involved in reactions that lead to the covalent attachment of the oxide, the extent of which depends on the carbon characteristics, heating rate, and mechanism. TiO2 is more efficiently stabilized at the surface of RGO than amorphous carbon. Rapid heating of the reaction mixture results in a stronger coupling between the nanoparticles and carbon, more uniform coatings, and smaller particles with narrower size distributions. The more efficient attachment of the oxide leads to better photocatalytic performance.
Phenol‐Substituted Tetrapyrazinoporphyrazines: pH‐Dependent Fluorescence in Basic Media
Authors: Novakova Veronika , Lásková Miroslava , Vavřičková Hana , Zimcik Petr
Published: August 2015

Tetrapyrazinoporphyrazines (TPyzPzs) bearing one, two, four or eight 3,5‐di(tert‐butyl)‐4‐hydroxyphenol moieties were synthesized as zinc(II) complexes and metal‐free derivatives. The deprotonation of the phenol using tetrabutylammonium hydroxide induced the formation of a strong donor for intramolecular charge transfer that switched OFF the red fluorescence (λF∼660 nm) of the parent zinc TPyzPzs. The changes were fully reversible for TPyzPzs with one to four phenolic moieties, and an irreversible modification was observed for TPyzPzs substituted with eight phenols. The sensors were anchored to lipophilic particles in water, and a pKa approximately 12.5–12.7 was determined for the phenolic hydroxyl based on fluorescence changes in different buffers. In addition, a novel concept for fluorescence OFF‐ON‐OFF switching in metal‐free TPyzPzs bearing phenolic moieties upon addition of specific amounts of base was demonstrated.
Einfluss der Partikelgröße und Partikelform auf das Fließverhalten von kommerziellen Magermilchpulvern
Authors: Schulnies Frank , Tilgner Lars , Kleinschmidt Thomas
Published: August 2015

Aufgrund der zahlreichen Verwendungsmöglichkeiten in der Lebensmittelproduktion nimmt Magermilchpulver unter den Trockenmilcherzeugnissen in Deutschland die größte wirtschaftliche Bedeutung ein. Für die problemlose Handhabung der Produkte ist ein adäquates Fließverhalten erforderlich. In der vorliegenden Arbeit wurde daher das Fließverhalten kommerzieller Magermilchpulver mithilfe von Scherversuchen charakterisiert, um die Handhabung besser einschätzen zu können. Durch die ergänzende Bestimmung der Partikelgrößen‐ und Formverteilungen wurden Zusammenhänge zum Fließverhalten herausgearbeitet.
Climate Change Impacts on Flow, Sediment and Nutrient Export in a Great Lakes Watershed Using SWAT
Authors: Verma Siddhartha , Bhattarai Rabin , Bosch Nathan S. , Cooke Richard C. , Kalita Prasanta K. , Markus Momcilo
Published: August 2015

This study aims at understanding the impacts of projected climate change on the hydrological processes within the Maumee River watershed (16 395 km2) lying in the Lake Erie Basin using soil and water assessment tool (SWAT). The model was calibrated and validated for a baseline time‐period of 1995–2005. Downscaled ensemble projected temperature and precipitation data from three general circulation models (GCMs) was then used to assess future flow, sediment, and nutrient loading in the watershed for mid‐century (2045–2055) and late‐century (2089–2099) time periods. Compared to the baseline, a 2.9°C rise in the annual average temperature along with a 3.2% fall in the annual precipitation in the mid‐century time‐period is projected to reduce annual flow volumes, and suspended solids (SS), total phosphorus (TP), nitrate (NO3) loads by 8.5, 10.4, 8.5, and 9.9%, respectively. Similarly, for the late‐century a 4.3°C rise in the annual average temperature along with a 5.6% rise in the annual precipitation is projected to increase annual flow volumes, and SS, TP, NO3loads by 9.7, 19.6, 3.5, and 6.8%, respectively. Temporal shifts in climatic conditions were also projected for both the future time‐periods with higher temperatures throughout the year along with wetter winters and drier summers. Implications of these changes would include the need for an increased focus on pollutant loadings for total maximum daily load guidelines and possible lengthening of crop growing cycles.
Spatio‐Temporal Variation of Chlorophyll‐a in a Drinking Water Reservoir: Role of Hydraulic Conditions and Inflow
Authors: Liu Hongbo , Pan Ding , Chen Piao
Published: August 2015

The temporal and spatial distribution of chlorophyll‐a in a shallow drinking water reservoir has been investigated. The chlorophyll‐a content in deeper zones varied from vertical stratification to de‐stratification during the study period. A higher frequency of occurrence for changes between high and low chlorophyll‐a values was found in the middle area of the reservoir compared to the border area. The magnitude of high/low values also differed seasonally and geographically. The reason for the variation of chlorophyll‐a in the reservoir was found as a complex result of the influence of water level, nutrients, water depth, temperature, and light as potential factors. The results indicate that the mixing effect triggered by inflow and other hydraulic conditions is one of the important factors influencing temporal and spatial variations of the chlorophyll‐a content in the reservoir.
Long‐term follow‐up of a phase 2 study of chemotherapy plus dasatinib for the initial treatment of patients with Philadelphia chromosome–positive acute lymphoblastic leukemia
Authors: Ravandi Farhad , O'Brien Susan M. , Cortes Jorge E. , Thomas Deborah M. , Garris Rebecca , Faderl Stefan , Burger Jan A. , Rytting Michael E. , Ferrajoli Alessandra , Wierda William G. , Verstovsek Srdan , Champlin Richard , Kebriaei Partow , McCue Deborah A. , Huang Xuelin , Jabbour Elias , Garcia‐Manero Guillermo , Estrov Zeev , Kantarjian Hagop M.
Published: August 2015

BACKGROUND

The long‐term efficacy of a combination of chemotherapy and dasatinib in patients with Philadelphia chromosome–positive (Ph+) acute lymphoblastic leukemia (ALL) is not well established.

METHODS

Patients received dasatinib with 8 cycles of alternating hyperfractionated cyclophosphamide, vincristine, doxorubicin, and dexamethasone and high‐dose cytarabine and methotrexate. Patients in complete remission (CR) continued maintenance dasatinib, vincristine, and prednisone for 2 years, which was followed by dasatinib indefinitely. Patients eligible for allogeneic stem cell transplantation (SCT) received it during their first CR.

RESULTS

Seventy‐two patients with a median age of 55 years (range, 21‐80 years) were treated; 69 (96%) achieved CR. Among them, 57 (83%) achieved cytogenetic CR after 1 cycle, and 64 (93%) achieved a major molecular response at a median of 4 weeks (range, 2‐38 weeks). Sixty‐five patients (94%) were negative for minimal residual disease assessed by flow cytometry at a median of 3 weeks (range, 2‐37 weeks). Dasatinib‐related grade 3 and 4 adverse events included bleeding, pleural/pericardial effusions, and elevated transaminases. With a median follow‐up of 67 months (range, 33‐97 months), 33 patients (46%) were alive, and 30 (43%) were in CR; 12 underwent allogeneic SCT. Thirty‐nine patients died (3 at induction, 19 after relapse, 7 after SCT performed during first CR, and 10 during CR). The median disease‐free survival and overall survival were 31 (range, 0.3‐97 months) and 47 months (range, 0.2‐97 months), respectively. Seven relapsed patients had BCR‐ABL kinase domain mutations, including 4 with T315I.

CONCLUSIONS

A combination of chemotherapy with dasatinib is effective in achieving long‐term remission for patients with newly diagnosed Ph + ALL. Cancer 2015;121:4158–4164. © 2015 American Cancer Society.
MicroRNA Regulation of Airway Inflammation and Airway Smooth Muscle Function: Relevance to Asthma
Authors: Deshpande DA , Dileepan M , Walseth TF , Subramanian S , Kannan MS
Published: August 2015

Preclinical Research

Genetic and environmental factors contribute to the onset and severity of asthma. Molecular pathogenesis of asthma involves changes in gene expression by a variety of inflammatory mediators acting in autocrine and paracrine fashion on effector cells of the airways. Transcriptional regulation of gene expression in resident airway cells has been studied extensively. However, protein function in a target cell can be regulated at multiple levels starting from transcription followed by post‐transcription, translation, and post‐translation steps. In this context, small noncoding RNAs known as microRNAs (miRNAs) have evolved as one of the key regulators of gene expression post‐transcriptionally. Most importantly, miRNA expression is dynamic in nature and can be regulated by a variety of external stimuli. Altered expression of individual or a group of miRNAs is thought to contribute to human diseases. Recent studies have implicated differential expression of miRNAs in the lungs during inflammation. Most importantly, advanced biochemical and molecular tools could be used to manipulate miRNA expression thereby effecting functional changes in target cells and organ systems. This review summarizes the current understanding of miRNA in the regulation of airway function in health and disease, and highlights the potential clinical utility of mRNAs as biomarkers of airway diseases and as potential therapeutic targets. Drug Dev Res 76 : 286–295, 2015. © 2015 Wiley Periodicals, Inc.
Foods, macronutrients and fibre in the diet of blue sheep (Psuedois nayaur) in the Annapurna Conservation Area of Nepal
Authors: Aryal Achyut , Coogan Sean C. P. , Ji Weihong , Rothman Jessica M. , Raubenheimer David
Published: August 2015

Food resources are often critical regulating factors affecting individual fitness and population densities. In the Himalayan Mountains, Bharal “blue sheep” (Pseudois nayaur) are the main food resource for the endangered snow leopard (Panthera uncia), as well as being preyed upon by other predators. Blue sheep, however, may face a number of challenges including food resource competition with other wild and domestic ungulates, and hunting pressure. Here, we characterized the diet of blue sheep in the Annapurna Conservation Area (ACA) of Nepal and conducted proximate nutritional analysis on a limited number of plants identified as foods. Furthermore, we investigated the macronutrient and fiber balance of these plants using nutritional geometry which is a state‐space approach to modeling multidimensional and interactive nutritional aspects of foraging. A total of 19 plant species/genera were identified in blue sheep pellets using microhistological analysis. On average, across seasons and regions of the study area, the two most frequently occurring plants in pellets were graminoids: Kobressia sp. and Carex spp. The macronutrient balance of Kobresia sp. was relatively high in carbohydrate and low in protein, while other plants in the diet were generally higher in protein and lipid content. Analysis of fiber balance showed that the two most consumed plants of blue sheep (i.e., Kobresia spp. and Carex spp.) contained the highest concentration of hemicellulose, which is likely digestible by blue sheep. The hemicellulose and lignin balance of plants ranged relatively widely, yet their cellulose contents showed less variation. Foraging by blue sheep may therefore be a balance between consuming highly digestible high‐carbohydrate plants and plants less‐digestible but higher in protein and/or lipid.
Monitoring the Hemolytic Effect of Mesoporous Silica Nanoparticles after Human Blood Protein Corona Formation
Authors: Martinez Diego Stéfani T. , Paula Amauri J. , Fonseca Leandro C. , Luna Luis Augusto V. , Silveira Camila P. , Durán Nelson , Alves Oswaldo L.
Published: August 2015

The interaction of promising nanoparticles with red blood cells (RBCs) is a critical point to be addressed in nanomedicine and nanotoxicology, and the hemolytic assay is a classical and common test used to evaluate such interactions and the consequent nanoparticle toxicity. In addition, the protein corona is an emergent concept in bionanoscience associated with the manifestation of energetically driven protein–nanoparticle interactions, with a great impact on the nanomaterial toxicity assessment. In the convergence of these two concepts, we evaluated the influence of the formation of the protein corona during the hemolysis induced by spherical mesoporous silica nanoparticles with silanol groups on the external surface (MSN‐SiOH), which present a confirmed toxicity on RBCs when they are dispersed as a colloid in phosphate buffer saline solution (PBS). It was observed that human blood proteins such as human serum albumin (HSA), human plasma (HP), hemoglobin (Hb), and RBC lysate, termed hemolysate (HL), can suppress the hemolytic effect induced by MSN‐SiOH in a dose‐dependent manner. The EC50 values of hemolysis suppression were 24, 8.0, 19, and 28 μg mL–1 for HSA, HP, Hb, and HL, respectively. This work thus shows that the results of the hemolytic assay that defines the toxicity and bioreactivity of silica nanoparticles (and others) must be interpreted as a function of the formation of the protein corona.
Automated Serendipity with Self‐Optimizing Continuous‐Flow Reactors
Authors: Amara Zacharias , Streng Emilia S. , Skilton Ryan A. , Jin Jing , George Michael W. , Poliakoff Martyn
Published: August 2015

A self‐optimizing approach is used as a tool for targeting known and unknown materials in the continuous reaction of aniline, dimethyl carbonate (DMC) and tetrahydrofuran (THF) in supercritical CO2 on γ‐Al2O3. The study led to the formation of methylated anilines or carbamate derivatives and unusual addition products with THF including pyrrolidines and N‐alkylated anilines. The identification of these products leads to the development of a plausible mechanism for the reactions. The system not only demonstrates a high flexibility that the self‐optimization approach provides, including the ability to optimize for a variety of products by using a single catalyst, but also the ability to discover unexpected and original synthetic reactions.
Manganese Oxide Nanoparticles/Reduced Graphene Oxide as Novel Electrochemical Platform for Immobilization of FAD and its Application as Highly Sensitive Persulfate Sensor
Authors: Mansouri Majd Samira , Salimi Abdollah , Astinchap Bandar
Published: August 2015

In this study, manganese oxide nanoparticles/reduced graphene oxide(MnOxNPs/rGO) was used as support for strong immobilization of flavin adenine dinucleotide(FAD). A thin film of rGO cast on the electrode surface, followed by performing electrodeposition of MnOxNPs at applied constant potential of +1.4 V vs. Ag/AgCl for 200 s. Finally, FAD was electrodeposited onto the rGO/MnOxNPs film by potential cycling between 1.0 to −1.0 V in solution containing 1 mg ml−1 FAD. Electrochemical properties and catalytic activity of GCE/rGO‐MnOxNPs/FAD toward persulfate (S2O82−) reduction was investigated. Under optimized condition, the concentration calibration range, detection limit, and sensitivity were 0.1 μM–2 mM, 90 nM and 125.8 nA/μM, respectively, using hydrodynamic amperometry technique.
Nonparametric species richness estimation under convexity constraint
Authors: Durot Cécile , Huet Sylvie , Koladjo François , Robin Stéphane
Published: August 2015

We consider the estimation of the number N of present species in a given area at a given time, based on the abundances of species that have been observed. We adopt a nonparametric approach where the true abundance distribution p is only supposed to be convex. A definition for convex abundance distributions is proposed. A least‐squares estimate of the truncated version of p under the convexity constraint is used. Two estimators of N are deduced, the asymptotic distribution of which are derived. We propose three different procedures, including a bootstrap one, to obtain a confidence interval for N and a standard error for its estimator. The performances of the estimators are assessed in a simulation study and compared with competitors. The proposed method is illustrated on several examples. Copyright © 2015 John Wiley & Sons, Ltd.
A new numerical model for simulations of wave transformation, breaking and long‐shore currents in complex coastal regions
Authors: Gallerano F. , Cannata G. , Lasaponara F.
Published: August 2015

In this paper, we propose a model based on a new contravariant integral form of the fully nonlinear Boussinesq equations in order to simulate wave transformation phenomena, wave breaking, and nearshore currents in computational domains representing the complex morphology of real coastal regions. The aforementioned contravariant integral form, in which Christoffel symbols are absent, is characterized by the fact that the continuity equation does not include any dispersive term. A procedure developed in order to correct errors related to the difficulties of numerically satisfying the metric identities in the numerical integration of fully nonlinear Boussinesq equation on generalized boundary‐conforming grids is presented. The Boussinesq equation system is numerically solved by a hybrid finite volume–finite difference scheme. The proposed high‐order upwind weighted essentially non‐oscillatory finite volume scheme involves an exact Riemann solver and is based on a genuinely two‐dimensional reconstruction procedure, which uses a convex combination of biquadratic polynomials. The wave breaking is represented by discontinuities of the weak solution of the integral form of the nonlinear shallow water equations.

The capacity of the proposed model to correctly represent wave propagation, wave breaking, and wave‐induced currents is verified against test cases present in the literature. The results obtained are compared with experimental measures, analytical solutions, or alternative numerical solutions. Copyright © 2015 John Wiley & Sons, Ltd.
Roe‐type Riemann solver for gas–liquid flows using drift‐flux model with an approximate form of the Jacobian matrix
Authors: da Silva Santim Christiano Garcia , Rosa Eugênio Spanó
Published: August 2015

This work presents an approximate Riemann solver to the transient isothermal drift‐flux model. The set of equations constitutes a non‐linear hyperbolic system of conservation laws in one space dimension. The elements of the Jacobian matrix A are expressed through exact analytical expressions. It is also proposed a simplified form of A considering the square of the gas to liquid sound velocity ratio much lower than one. This approximation aims to express the eigenvalues through simpler algebraic expressions. A numerical method based on the Gudunov's fluxes is proposed employing an upwind and a high order scheme. The Roe linearization is applied to the simplified form of A. The proposed solver is validated against three benchmark solutions and two experimental pipe flow data. Copyright © 2015 John Wiley & Sons, Ltd.
Efficient production of poly‐γ‐glutamic acid from cane molasses by Bacillus subtilisNX‐2 immobilized on chemically modified sugarcane bagasse
Authors: Feng Xiaohai , Tang Bao , Jiang Yongxiang , Xu Zongqi , Lei Peng , Liang Jinfeng , Xu Hong
Published: August 2015

BACKGROUND

Poly‐γ‐glutamic acid (PGA), a naturally occurring homopolymer, has gained increased interest worldwide because of its extensive applications. In this study, sugarcane bagasse chemically modified with poly‐ϵ‐L‐lysine (PL) was used in an aerobic plant fibrous‐bed bioreactor (APFB) to enhance PGA fermentation by Bacillus subtilis NX‐2.

RESULTS

5 g L−1 of PL was optimized to modify native sugarcane bagasse, and 45.7 ± 0.6 g L−1 PGA was obtained with PL‐bagasse immobilized cells in batch fermentation, with a productivity of 1.08 ± 0.02 g L−1 h−1. These results were 1.23 and 1.4 times higher than those with unmodified sugarcane bagasse. The effect of dissolved oxygen (DO) on PGA fermentation was further investigated, and suitable conditions were 45% DO with the PGA concentration 55.4 ± 0.4 g L−1. In 10 batches of repeated‐batch fermentation, PGA production significantly increased and the average PGA yield was maintained at 90.6 ± 0.5 g L−1 in the three later batches and was increased by 8.7% compared with that in the first batch.

CONCLUSION

The improved APFB system was proved to be a green, economic, and effective bioprocess for PGA fermentation, and this system could also provide a suitable microenvironment for B. subtilis NX‐2 to induce its evolution. © 2015 Society of Chemical Industry
A novel synthesis of isoeugenol, [ring‐(U)‐14C]
Authors: Immoos John E.
Published: August 2015

A novel method for the preparation of isoeugenol, [ring‐(U)‐14C] is presented. Phenols and phenyl esters substituted in the para position with 1‐hydroxyethyl or 1‐hydroxypropyl acetate esters when treated with 1,8‐diazabicyclo[5.4.0]undec‐7‐ene in dimethylformamide (DMF) eliminate the alkyl carboxylate function to give the unsaturated compound. The reaction fails with unsubstituted or ether substituted phenyl 1‐hydroxyacetate esters.
Mechanical properties and structure–function relationships in articular cartilage repaired using IGF‐I gene‐enhanced chondrocytes
Authors: Griffin Darvin J. , Ortved Kyla F. , Nixon Alan J. , Bonassar Lawrence J.
Published: August 2015

Several studies have demonstrated the benefits of IGF‐I gene therapy in enhancing the histologic and biochemical content of cartilage repaired by chondrocyte transplantation. However, there is little to no data on the mechanical performance of IGF‐I augmented cartilage grafts. This study evaluated the compressive properties of full‐thickness chondral defects in the equine femur repaired with and without IGF‐I gene therapy. Animals were randomly assigned to one of three study cohorts based on chondrocyte treatment provided in each defect: (i) IGF‐I gene delivered by recombinant adeno‐associated virus (rAAV)‐5; (ii) AAV‐5 delivering GFP as a reporter; (iii) naïve cells without virus. In each case, the opposite limb was implanted with a fibrin carrier without cells. Samples were prepared for confined compression testing to measure the aggregate modulus and hydraulic permeability. All treatment groups, regardless of cell content or transduction, had mechanical properties inferior to native cartilage. Overexpression of IGF‐I increased modulus and lowered permeability relative to other treatments. Investigation of structure–property relationships revealed that Ha and k were linearly correlated with GAG content but logarithmically correlated with collagen content. This provides evidence that IGF‐I gene therapy can improve healing of articular cartilage and can greatly increase the mechanical properties of repaired grafts. © 2015 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 34:149–153, 2016.