bluuebunny/crossref_metadata_2025 huggingface dataset:
Activation of Dioxygen at a Lewis Acidic Nickel(II) Complex: Characterization of a Metastable Organoperoxide Complex
Authors: Holze Patrick , Corona Teresa , Frank Nicolas , Braun‐Cula Beatrice , Herwig Christian , Company Anna , Limberg Christian
Published: January 2017

In metal‐mediated O2 activation, nickel(II) compounds hardly play a role, but recently it has been shown that enzymes can use nickel(II) for O2 activation. Now a low‐coordinate Lewis acidic nickel(II) complex has been synthesized that reacts with O2 to give a nickel(II) organoperoxide, as proposed for the enzymatic system. Its formation was studied further by UV/Vis absorption spectroscopy, leading to the observation of a short‐lived intermediate that proved to be reactive in both oxygen atom transfer and hydrogen abstraction reactions, while the peroxide efficiently transfers O atoms. Both for the enzyme and for the functional model, the key to O2 activation is proposed to represent a concomitant electron shift from the substrate/co‐ligand.
Enantioselective Copper‐Catalyzed Intermolecular Amino‐ and Azidocyanation of Alkenes in a Radical Process
Authors: Wang Dinghai , Wang Fei , Chen Pinghong , Lin Zhenyang , Liu Guosheng
Published: January 2017

Asymmetric copper‐catalyzed intermolecular amino‐ and azidocyanation reactions of alkenes have been developed that proceed via a radical process in which a key benzylic radical intermediate is enantioselectively trapped by a chiral Box/CuII cyanide complex. A variety of enantiomerically enriched β‐amino/azido alkylnitriles were efficiently synthesized. The β‐azido alkylnitriles could be converted into a series of highly valuable optically active amine‐based building blocks and bioactive compounds.
Synthesis of Boron(III)‐Coordinated Subchlorophins and Their Peripheral Modifications
Authors: Yoshida Kota , Cha Wonhee , Kim Dongho , Osuka Atsuhiro
Published: January 2017

A pyrrole‐cleaving modification to transform boron(III) meso‐triphenylsubporphyrin into boron(III) meso‐triphenylsubchlorophin has been developed. Boron(III) subchlorophins thus synthesized show absorption and fluorescence spectra that are roughly similar to those of boron(III) subchlorins, but B‐methoxy boron(III) subchlorophin showed considerably intensified fluorescence and a small Stokes shift. Peripheral modification reactions of B‐phenyl boron(III) subchlorophin such as regioselective nitration with Cu(NO3)2⋅3 H2O, ipso‐substitution reactions of boron(III) α‐nitrosubchlorophin with CsF and CsCl, and Pd‐catalyzed cross‐coupling reactions of boron(III) α‐chlorosubchlorophin with arylacetylenes, have been also explored to tune the optical properties of subchlorophins.
Nickel(0)‐Mediated Transformation of Tetrafluoroethylene and Vinylarenes into Fluorinated Cyclobutyl Compounds
Authors: Ohashi Masato , Ueda Yuta , Ogoshi Sensuke
Published: January 2017

In the presence of Ni0/PCy3, styrene was found to participate in oxidative cyclization with tetrafluoroethylene, thus leading to the corresponding nickelacycle with a unique η3‐π‐benzyl structure. In addition, the flexibility of the coordination mode in the η3‐benzyl moiety allowed the partially fluorinated nickelacycle to undergo unprecedented amine‐induced α‐fluorine elimination, thus leading to the construction of a fluorinated cyclobutyl skeleton.
Accessing the Intrinsic Nature of Electronic Transitions from Gas‐Phase Spectroscopy of Molecular Ion/Zwitterion Complexes
Authors: Stockett Mark H. , Boesen Mikkel , Houmøller Jørgen , Brøndsted Nielsen Steen
Published: January 2017

A molecule's color is governed by the nature of its electronic transitions. Herein we show that the degree of charge transfer can be assessed by measuring the change in absorption induced by complexation with the betaine zwitterion. Our approach benefits from direct formation of complexes by electrospray of a mixture solution, followed by photodissociation action spectroscopy. We explored two ion groups: 1) No permanent dipole moment due to even charge delocalization (e.g. MnO4−) and 2) Non‐even charge distribution but where the charge according to resonance forms is either delocalized (e.g. oxyluciferin) or located at one site (e.g. m‐nitrophenolate, mNP). The maximal shift for ions from (1) was <0.05 eV but as large as 0.3 eV and 0.2 eV for mNP and oxyluciferin. Hence our work supports the notion that oxyluciferin undergoes CT, and that the microenvironment can account for large variation in light emission from insects, ranging from green to red (shift of 0.3 eV).
Morphology control of conducting polypyrrole nanostructures via operational conditions in the emulsion polymerization
Authors: Khadem Fatemeh , Pishvaei Malihe , Salami‐Kalajahi Mehdi , Najafi Farhood
Published: January 2017

Polypyrrole (PPy) nanostructures with diameter smaller than 100 nm were synthesized by chemical oxidative polymerization of pyrrole in the presence of cetyl trimethylammonium bromide and sodium dodecyl sulfate as surfactants. Hydrochloric acid was used as dopant, and a solution of potassium peroxydisulfate was used as initiator. The influence of polymerization temperature, feeding strategy, and the type of surfactant on the morphology and conductivity of PPy nanostructures were investigated and well‐described. A simple route just via controlling the operational conditions in the emulsion polymerization is reported to obtain nanostructured PPy with desirable morphology and relatively good conductivity. The analysis results demonstrated that the conductivity of samples is highly affected by their morphology whereas PPy nanofibers exhibited higher conductivity respecting the other morphologies (0.66 S/cm). © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44697.
Photochromic properties of color‐matching, double‐shelled microcapsules covalently bonded onto cotton fabric and applications to outdoor clothing
Authors: Fan Fei , Wu Yingzhu
Published: January 2017

In this research, we aimed to apply color‐matching, double‐shelled microcapsules to deal with outdoor‐clothing sunscreen‐indicator identifications on cotton fabrics with a covalent‐bonding coating method; this method allows one to display both the UV intensity and a warning. The color‐property characteristics of color‐matching‐double‐shelled‐photochromic‐microcapsule–treated patterns on cotton fabrics under various sunshine irradiation intensities are very close to those of inkjet‐printing color‐gradation patterns, which indicate sunshine irradiation intensities. Color‐matching, double‐shelled microcapsules were obtained by the addition of red double‐shelled microcapsules into yellow double‐shelled microcapsules. We increased the weight ratio of the red microcapsules and added blue double‐shelled microcapsules into the red double‐shelled microcapsules when the weight ratio of blue microcapsules was increased. Color‐matching, double‐shelled photochromic microcapsules, whose yellow/red/blue weight ratios were 5.6/0/0, 4.8/0.8/0, 2.4/3.2/0, and 0.8/4.8/0–0/0/5.6, presented distinct color‐property characteristic changes under various irradiation intensities and presented a good color identification; a rather dark, bright color; and good laundering durability of covalent bonding on cotton fabrics. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44698.
Polypropylene with high melt flow rate and high isotacticity prepared by phosphate‐mixed external donors
Authors: Zhou Qian , Xu Hao , Wang Ailian , Ma Zhifeng , Li Huayi , Zhang Liaoyun , Hu Youliang
Published: January 2017

High melt flow rate (MFR) of polypropylene can improve its processability and its high isotacticity is favor of keeping good mechanical properties of polypropylene. In this study, as a convenient and effective method, the mixture of phosphate and alkoxysilane as mixed external donors for Ziegler‐Natta catalyst is used to improve MFR of polypropylene. The MFR of polypropylenes prepared by mixed external donors is three to five time higher than that prepared by dicyclopentyl dimethoxysilane (Donor‐D) alone, which is attributed to broad molecular weight distribution and low molecular weight of polypropylene prepared by mixed external donors. In addition, isotacticity and lamella thickness of polypropylene prepared by mixed external donors containing triisopropyl phosphate or phenyl‐phosphonic acid dipentyl ester are very close to that prepared by Donor‐D, which lead to keep high thermal properties and good mechanical properties for the polypropylenes. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44704.
Cellulose nanofibrils in biobased multilayer films for food packaging
Authors: Vähä‐Nissi Mika , Koivula Hanna M. , Räisänen Heidi M. , Vartiainen Jari , Ragni Pietro , Kenttä Eija , Kaljunen Timo , Malm Tero , Minkkinen Hannu , Harlin Ali
Published: January 2017

The aim of this study was to evaluate a thin, TEMPO‐oxidized (2,2,6,6‐tetramethylpiperidine‐1‐oxyl–mediated oxidation) cellulose nanofibril (CNF) coating as a barrier layer in multilayer packaging films together with biobased polyethylenes. The purpose was also to explore the possible interactions between food products and the biobased films, and to evaluate the feasibility of these films for packaging of dry foods. CNF provided the biobased multilayer films with an oxygen barrier suitable for both demanding food products and modified atmosphere packaging (MAP). The MAP pouches made of these multilayer films retained their atmosphere and shape and protected ground hazelnuts from further oxidation for the storage time used in this study. However, irradiation used to sterilize packed foods and aroma compounds from clove in particular impaired the oxygen barrier property of the CNF layer, while the water vapor barrier property of the multilayer films remained unaffected. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44830.
Zirconium Hydroxide‐coated Nanofiber Mats for Nerve Agent Decontamination
Authors: Kim Sohee , Ying Wu Bin , Jung Hyunsook , Ryu Sam Gon , Lee Bumjae , Lee Kyung Jin
Published: January 2017

Diverse innovative fabrics with specific functionalities have been developed for requirements such as self‐decontamination of chemical/biological pollutants and toxic nerve agents. In this work, Zr(OH)4‐coated nylon‐6,6 nanofiber mats were fabricated for the decontamination of nerve agents. Nylon‐6,6 fabric was prepared via the electrospinning process, followed by coating with Zr(OH)4, which was obtained by the hydrolysis of Zr(OBu)4 by a sol–gel reaction on nanofiber surfaces. The reaction conditions were optimized by varying the amounts of Zr(OBu)4,the reaction time, and the temperature of the sol–gel reaction. The composite nanofibers show high decontamination efficiency against diisopropylfluorophosphate, which is a nerve agent analogue, due to its high nucleophilicity that aids in the catalysis of the hydrolysis of the phosphonate ester bonds. Composite nanofiber mats have a large potential and can be applied in specific fields such as military and medical markets.
Impact of completeness of revascularization in complex coronary artery disease as measured with the SYNTAX revascularization index: An SEEDS Substudy
Authors: Xu Bo , Bettinger Nicolas , Guan Changdong , Redfors Björn , Yang Yuejin , Li Bao , Han Yaling , Su Xi , Yuan Zuyi , Généreux Philippe
Published: January 2017

Objectives

We sought to study whether the level of completeness of revascularization as measured by the SYNTAX revascularization index (SRI) independently predicts adverse ischemic events after percutaneous coronary intervention (PCI) with second‐generation drug‐eluting stents (DES).

Background

The SRI quantifies the proportion of revascularized myocardium. It has been shown to independently predict adverse ischemic events after PCI with first‐generation DES.

Methods

Among 1,900 patients enrolled in a registry to evaluate safety and effectiveness of everolimus drug‐eluting stent (SEEDS) for coronary revascularization, the SRI was calculated and available for 1,851 patients. The patients were stratified into three groups according to the degree of revascularization (SRI = 100% [complete revascularization], SRI = 50 to <100%, and SRI <50%). Two‐year mortality and major adverse cardiac events (MACE) were compared between the groups.

Results

The SRI ranged from 4–100%, with a mean of 85.4%. Complete revascularization was achieved in 1,190 patients, while the SRI was 50% to <100% in 472 patients and <50% in 189 patients. Two‐year mortality and MACE rates were higher in patients with lower SRI. ROC analysis showed an optimal SRI cutoff of 85% for predicting the 2‐year mortality risk. An SRI ≥85% was associated with a similar risk of death to complete revascularization. The SRI independently predicted 2‐year mortality and MACE.

Conclusions

The SRI predicts mortality and adverse ischemic events in patients with complex CAD who underwent contemporary PCI with second‐generation DES. Revascularizing ≥85% of the CAD burden was associated with a good prognosis and should be considered as a reasonable goal. © 2017 Wiley Periodicals, Inc.
A propensity score matched comparative study between paclitaxel‐coated balloon and everolimus‐eluting stents for the treatment of small coronary vessels
Authors: Giannini Francesco , Latib Azeem , Ancona Marco B. , Costopoulos Charis , Ruparelia Neil , Menozzi Alberto , Castriota Fausto , Micari Antonio , Cremonesi Alberto , De Felice Francesco , Marchese Alfredo , Tespili Maurizio , Presbitero Patrizia , Sgueglia Gregory A. , Buffoli Francesca , Tamburino Corrado , Varbella Ferdinando , Colombo Antonio
Published: January 2017

Objectives

To compare the long‐term clinical outcomes of paclitaxel drug‐coated‐balloons (DCB) and everolimus‐eluting‐stents (EES) following the treatment of de novo small vessel coronary artery disease.

Background

It is currently unclear whether treatment of de novo small vessel coronary disease with DCB is comparable to second generation drug‐eluting stents, which are the current standard of care.

Methods

The present study enrolled 90 patients with small vessel coronary disease from the DCB treatment arm of the BELLO (Balloon Elution and Late Loss Optimization) trial and 2,000 patients treated with EES at the San Raffaele Scientific Institute. Propensity score matching was performed to adjust for differences in baseline clinical and angiographic characteristics, yielding a total of 181 patients: 90 patients with 94 lesions receiving DCB and 91 patients with 94 lesions receiving EES. Major adverse cardiac events (MACE) were defined as the composite of cardiac death, recurrent non‐fatal myocardial infarction, and target vessel revascularization.

Results

After propensity score matching, baseline clinical and angiographic characteristics were similar between the two groups. The cumulative MACE rate at 1‐year was 12.2% with DCB and 15.4% with EES (P = 0.538). Patients in the DCB group had similar TLR rates as compared to EES over the same interval (4.4% vs. 5.6%; P = 0.720). There were no cases of definite or probable stent or vessel thrombosis.

Conclusions

The use of paclitaxel‐DCB appears to be associated with similar clinical outcomes when compared to second‐generation‐EES in small coronary artery disease. The findings of this study should be confirmed with larger prospective randomized studies with longer follow‐up. © 2017 Wiley Periodicals, Inc.
Prolonged QT interval and cardiac arrest after a single dose of amiodarone in a woman with Turner's syndrome
Authors: Nielsen Dorte Guldbrand , Nielsen Jens Cosedis , Trolle Christian , Gravholt Claus Højbjerg , Andersen Niels Holmark
Published: January 2017

Key Clinical Message

Low‐dose QT‐prolonging drugs may have detrimental effects on women with Turner's syndrome. Preventive measures would be to use potential QT‐prolonging drugs with precaution and ensure that both before and during treatment, ECGs are evaluated and drug treatment stopped if the QT interval increases.
Synthesis and Characterization of Three‐Dimensional Porous Cu@Pt and Cu@Pt‐Ru Catalysts for Methanol Oxidation
Authors: Alvarez Andrea E. , Sieben Juan Manuel , Duarte Marta M. E.
Published: January 2017

Highly porous Cu foams comprised of interconnected branched dendrites were used as sacrificial templates for the fabrication of pseudo core–shell Cu@Pt and Cu@Pt‐Ru unsupported electrodes by galvanic replacement. The as‐prepared materials presented a three‐dimensional structure with pores between 17 and 45 μm made of superimposed layers of ramified dendrites. TEM analysis showed that the dendrites were composed of agglomerates of grains of about 4 nm in size and mesopores of ca. 30 nm in diameter. The as‐prepared 3D electrodes were tested for methanol oxidation in acid media at different temperatures. The results showed that the catalytic activities of Cu@Pt and Cu@Pt‐Ru foams normalized to the electrochemical surface area are almost 50 % higher than that of a commercial Pt−Ru/C material, with poisoning rates that are reduced by half in the same potential range. The enhanced behavior of the as‐prepared foams is believed to be the result of the influence of copper atoms on the reactivity of platinum sites, the highly defective structure of the electrodes, as well as the facilitated diffusion of methanol molecules and the products formed during the reaction throughout the highly porous three‐dimensional structure of the electrode. The apparent activation energies (Ea,app) for the methanol oxidation reaction (MOR) were determined by potentiostatic experiments. Ea,app values of 29.07 and 24.20 kJ mol−1 were calculated for Cu@Pt and Cu@Pt‐Ru foams at 0.3 V, respectively. The results suggested that the MOR is governed by the dissociative adsorption of methanol as a result of the multifunctional nature of the catalyst and the facilitated diffusion of the products formed during the reaction.
Highly Active Noble‐Metal‐Free Copper Hydroxyapatite Catalysts for the Total Oxidation of Toluene
Authors: Chlala Dayan , Giraudon Jean‐Marc , Nuns Nicolas , Labaki Madona , Lamonier Jean‐François
Published: January 2017

Hydroxyapatite (Hap) supported Cu materials prepared by the wet impregnation method were designed as noble‐metal‐free catalysts for the total oxidation of toluene. Cu/Hap materials with different Cu loadings (2.5–20 wt %) calcined at 400 °C were characterized by using inductively coupled plasma optical emission spectroscopy, N2 physisorption, XRD, Raman spectroscopy, IR spectroscopy, X‐ray photoelectron spectroscopy, and time‐of‐flight secondary ion MS. The tenorite CuO phase was detected in all materials, and the libethenite Cu2(PO4)OH phase was observed for the sample with 20 wt % Cu. The presence of libethenite was accompanied by the formation of Ca2CO3H+ ions at the Hap surface. Residual NO3− species that interact with Cu and Ca were also found, and their amount increased with the increase of the Cu content in the sample. Interestingly, the specific activity in the total oxidation of toluene increased with the decrease of the Cu content in the catalyst. The rate per mole of Cu was increased by 10 times if the Cu content was decreased by four times. This noticeable result could be related to the presence of acid sites with a moderate strength as well as finely dispersed CuO species on the Hap, which allow the activation of toluene molecules and their oxidation through a redox mechanism. Moreover, Cu2.5 wt %/Hap showed a remarkably stable catalytic performance for 45 h time‐on‐stream, which evidences that this material has a high potential for applications in the removal of volatile organic compounds.
Effects of Charge Transfer on the Adsorption of CO on Small Molybdenum‐Doped Platinum Clusters
Authors: Ferrari Piero , Vanbuel Jan , Tam Nguyen Minh , Nguyen Minh Tho , Gewinner Sandy , Schöllkopf Wieland , Fielicke André , Janssens Ewald
Published: January 2017

The interaction of carbon monoxide with platinum alloy nanoparticles is an important problem in the context of fuel cell catalysis. In this work, molybdenum‐doped platinum clusters have been studied in the gas phase to obtain a better understanding of the fundamental nature of the Pt–CO interaction in the presence of a dopant atom. For this purpose, Ptn+ and MoPtn−1+ (n=3–7) clusters were studied by combined mass spectrometry and density functional theory calculations, making it possible to investigate the effects of molybdenum doping on the reactivity of platinum clusters with CO. In addition, IR photodissociation spectroscopy was used to measure the stretching frequency of CO molecules adsorbed on Ptn+ and MoPtn−1+ (n=3–14), allowing an investigation of dopant‐induced charge redistribution within the clusters. This electronic charge transfer is correlated with the observed changes in reactivity.
Synthesis of Nucleosides through Direct Glycosylation of Nucleobases with 5‐O‐Monoprotected or 5‐Modified Ribose: Improved Protocol, Scope, and Mechanism
Authors: Downey A. Michael , Pohl Radek , Roithová Jana , Hocek Michal
Published: January 2017

Simplifying access to synthetic nucleosides is of interest due to their widespread use as biochemical or anticancer and antiviral agents. Herein, a direct stereoselective method to access an expansive range of both natural and synthetic nucleosides up to a gram scale, through direct glycosylation of nucleobases with 5‐O‐tritylribose and other C5‐modified ribose derivatives, is discussed in detail. The reaction proceeds through nucleophilic epoxide ring opening of an in situ formed 1,2‐anhydrosugar (termed “anhydrose”) under modified Mitsunobu reaction conditions. The scope of the reaction in the synthesis of diverse nucleosides and other 1‐substituted riboside derivatives is described. In addition, a mechanistic insight into the formation of this key glycosyl donor intermediate is provided.
Triazole‐Based Anion‐Binding Catalysis for the Enantioselective Dearomatization of N‐Heteroarenes with Phosphorus Nucleophiles
Authors: Fischer Theresa , Duong Qui‐Nhi , García Mancheño Olga
Published: January 2017

The first enantioselective synthesis of chiral heterocyclic α‐amino phosphonates by nucleophilic dearomatization of quinolines and pyridines using an anion‐binding organocatalysis approach is described. Chiral tetrakistriazoles were employed as efficient hydrogen‐bond donor catalysts by forming a chiral close ion‐pair with the in situ formed N‐acyl salts and 2,2,2‐trichlorethoxycarbonyl chloride (TrocCl). The ion‐pair was subsequently treated with various phosphorus nucleophiles, such as silyl‐protected dialkyl‐ and trialkylphosphites. Thus, the corresponding products were obtained in complete or high regioselectivities and up to 97:3 e.r. for quinolines or up to 89:11 e.r. for the more challenging pyridine substrates. This method allows for rapid access to substituted chiral cyclic α‐amino phosphonates, which can be easily transformed into phosphonic acid derivatives.
Modelling, simulation, and membrane wetting estimation in gas‐liquid contacting processes
Authors: Pantoleontos Grigorios , Theodoridis Theodoros , Mavroudi Maria , Kikkinides Eustathios S. , Koutsonikolas Dimitrios , Kaldis Sotirios P. , Pagana Adamantia E.
Published: January 2017

A set of experiments for CO2 separation from CO2‐N2 mixture by absorption into water by means of a gas‐liquid membrane contacting process is modelled using the mass continuity equation by combining process conditions, membrane and fluids properties, and module geometric characteristics. The general case of non‐constant concentration of the diffusing component in the shell side (Case B) is used, which entails an integro‐differential boundary condition at the lumen‐wall. The computational method is compared with existing literature data in terms of the logarithmic averaged overall and lumen Sherwood numbers revalidating the superiority of the counter‐current to the co‐current mode of operation, while offering a theoretical prediction of the limited behaviour of the latter as a function of the equilibrium coefficient. The elaborate model is then applied in order to assess the extent of membrane wetting due to liquid penetration into the pores in terms of the resistance‐in‐series model by comparing with the experimental results derived in a commercial cross‐flow membrane module under the counter‐current mode of operation. It is revealed that the assumption of shell‐side constant concentration (Case A) underestimates the wetting leading to a false estimation of the extent of liquid penetration into membrane pores. For Case B, a wetting‐pattern appears showing a correlation of an increasing shell‐side liquid flow rate with a decreasing wetting parameter and, thus, relatively less contribution of the liquid‐filled membrane resistance to the overall membrane resistance with increasing liquid loading.
Effect of nitrogen doping on the catalytic activity of activated carbon and distribution of oxidation products in catalytic wet oxidation of phenol
Authors: Yang Guo , Chen Honglin , Qin Hangdao , Zhang Xiaoming , Feng Yujun
Published: January 2017

Nitrogen‐containing functional groups were introduced into activated carbon (AC) by amination at high temperatures to investigate their effects on the catalytic activity and distribution of products in the catalytic wet air oxidation (CWAO) of phenol at 120 and 160 °C. The results show that the catalytic activity of the nitrogen‐doped AC increases with amination temperature from 250 to 850 °C. The linear relationship between the quantity of nitrogen‐containing functional groups and the catalytic activity indicates that the enhanced activities are closely related to the amount of pyridinic and pyrrolic nitrogen groups on the surface of the AC. The parent and aminated AC exhibit distinct distributions of oxidation products. Oxalic acid is favourably degraded on the aminated AC, whereas the all‐carbon AC shows a similar ability for the removal of acetic acid.
A NEW METHOD FOR DROUGHT MONITORING BASED ON LAND SURFACE ENERGY BALANCE AND ITS PRELIMINARY APPLICATION TO THE HEDONG REGION OF GANSU PROVINCE
Authors: Xiao‐Cui HAO , Qiang ZHANG , Ze‐Su YANG , Xiao‐Wei WANG , Ping YUE , Tao HAN , Sheng WANG
Published: January 2017

Current drought monitoring methods based on remote sensing technique generally are not of high precision. Seeking a new remote sensing drought monitoring technique is of great help to improve and develop the technique of drought monitoring and alert. The Bowen ratio, the ratio of sensible heat flux against latent heat flux, and reflecting surface hydro‐thermal characteristics can be tentatively utilized for drought monitoring. Using EOS‐MODIS satellite data and synchronized meteorological data, the Bowen ratio drought monitoring model was established based on surface energy balance. Then, the correlation between soil moisture against Bowen ratio index (β) and temperature‐vegetation index (TVX) was analyzed. Finally, taking the clear‐sky imagery (October 5, 2014) as an example, a drought level classification standard based on β was established and droughts in the study region were evaluated. Results show that β is highly negatively related to soil relative humidity, which has a better correlation than that between TVX and soil relative humidity in the depth range of 0∼20 cm. The precision of drought monitoring is significantly improved. The distribution of dry‐wet condition based on the β drought classification standard is well consistent with the distribution of antecedent precipitation over the study region. Evaluation results show that generally no drought took place over the study region on October 5, 2014, which is consistent with precipitation anomaly percentage for the period of September, 2014. Our study suggests that the surface energy balance based Bowen ratio index can achieve excellent results when applied to drought monitoring and has a good application prospect.
Controlled Generation of Ultrathin‐Shell Double Emulsions and Studies on Their Stability
Authors: Zhao Chun‐Xia , Chen Dong , Hui Yue , Weitz David A. , Middelberg Anton P. J.
Published: January 2017

Double emulsions with a hierarchical core–shell structure have great potential in various applications, but their broad use is limited by their instability. To improve stability, water‐in‐oil‐in‐water (W/O/W) emulsions with an ultrathin oil layer of several hundred nanometres were produced by using a microcapillary device. The effects of various parameters on the generation of ultrathin‐shell double emulsions and their droplet size were investigated, including the proper combinations of inner, middle and outer phases, flow rates and surfactants. The surfactant in the middle oil phase was found to be critical for the formation of the ultrathin‐shell double emulsions. Furthermore, the stability of these double emulsions can be notably improved by increasing the concentration of the surfactant, and they can be stable for months. This opens up new opportunities for their future applications in cosmetics, foods and pharmaceuticals.
Composite mantle cell lymphoma and chronic lymphocytic leukemia/small lymphocytic lymphoma
Authors: Sun Yi , Wang Sa A. , Sun Tsieh
Published: January 2017

Background

Composite mantle cell lymphoma (MCL) and chronic lymphocytic leukemia/small lymphocytic lymphoma (CLL/SLL) is rare, as less than 20 cases have been reported so far. However, this entity may be under‐diagnosed because the two lymphomas are very similar in morphology and immunophenotype. Previous cases were mostly diagnosed with immunohistochemistry, but flow cytometry may play an important role in the detection of two tumors in the same specimen, thus achieving an accurate diagnosis. By definition, a composite lymphoma is two demarcated lymphomas occurring at the same anatomic site. Therefore, immunohistochemistry is still needed to identify the topographic relation of these two tumors. Our reported case illustrates the pitfalls in the diagnostic process and we recommend two standard panels with new markers for an accurate diagnosis of this composite lymphoma.

Method

FACSCanto II is used with antibodies, including CD5, CD10, CD19, CD20, CD22, CD23, CD43, CD79b, CD200, kappa, and lambda. Immunohistochemical stains include PAX‐5/CD5 dual stain, Cyclin D1, SOX11, and LEF‐1.

Results

CLL/SLL is positive for CD5, CD19, CD23, CD43, and CD200, with dim expression of CD20, CD22, CD79b, and kappa. MCL is positive for CD5, CD19, CD20, CD22, CD79b, kappa, and negative for CD23, CD43, and CD200. Immunohistochemical stains show that PAX‐5/CD5 stains the entire tumor population. Cyclin D1 and SOX11 only stain the central portion that represents MCL and LEF‐1 stains the periphery that represents CLL/SLL.

Conclusions

We recommend the use of the above panels for flow cytometry and immunohistochemistry, respectively. LEF‐1 is specific for CLL/SLL; and CD200 is helpful to distinguish CLL/SLL from MCL. © 2017 International Clinical Cytometry Society
Urothelial generation and regeneration in development, injury, and cancer
Authors: Wang Caihong , Ross Whitney Trotter , Mysorekar Indira U.
Published: January 2017

Homeostatic maintenance and repair of the urothelium upon injury are required for a functional bladder in both healthy and disease conditions. Understanding the cellular and molecular mechanisms underlying the urothelial regenerative response is key to designing strategies for tissue repair and ultimately treatments for urologic diseases including urinary tract infections, voiding dysfunction, painful bladder syndrome, and bladder cancer. In this article, we review studies on urothelial ontogeny during development and regeneration following various injury modalities. Signaling pathways involved in urothelial regeneration and in urothelial carcinogenesis are also discussed. Developmental Dynamics 246:336–343, 2017. © 2016 Wiley Periodicals, Inc.
Assessing the hydroxyl radical and volatilization roles in aquatic fate estimations of sulfur heterocycles: Dibenzothiophene derivatives
Authors: Saranjampour Parichehr , Armbrust Kevin L. , Marx Brian D.
Published: January 2017

Polycyclic aromatic sulfur heterocycles (PASHs) and their alkyl derivatives can be released into aquatic systems via crude oil spills or runoff from petroleum-treated areas, such as asphalt. Dibenzothiophene (DBT) and its derivatives (C1-DBT, C2-DBT, and C4-DBT) were chosen as model compounds to investigate the relative impact of volatilization and hydroxyl radical degradation on estimates of their overall dissipation after entry into aquatic ecosystems as a function of depth using the exposure analysis modeling system (EXAMS). The hydroxyl radical rate constant (K · OH) and Henry's law constant of PASHs were determined in distilled water. The analogue C1-DBT reacted fastest with · OH relative to other PASHs. The C2-DBT and C4-DBT analogues had higher Henry's law constants compared with other derivatives. Steric hindrance by alkyl substituents on the sulfur moiety most strongly impacted measured rate and Henry's law constants between DBT and individual alkyl derivatives. These steric effects do not appear to be considered in the physical property estimation software EPI Suite. Simulated dissipation of PASHs using EXAMS suggests that volatilization is a dominant fate pathway for the higher molecular weight and less polar C2-DBT and C4-DBT at all depths and DBT and C1-DBT at 0.1-m. However, model scenarios suggest that hydroxyl radical degradation may significantly contribute to the degradation of more polar DBT and C1-DBT at 1-m and 2-m depths. Environ Toxicol Chem 2017;36:1998–2004. © 2017 SETAC
Effects of metals on enantioselective toxicity and biotransformation of cis-bifenthrin in zebrafish
Authors: Yang Ye , Ji Dapeng , Huang Xin , Zhang Jianyun , Liu Jing
Published: January 2017

Co-occurrence of pyrethroids and metals in watersheds previously has been reported to pose great risk to aquatic species. Pyrethroids are a class of chiral insecticides that have been shown to have enantioselective toxicity and biotransformation. However, the influence of metals on enantioselectivity of pyrethroids has not yet been evaluated. In the present study, the effects of cadmium (Cd), copper (Cu), and lead (Pb) on the enantioselective toxicity and metabolism of cis-bifenthrin (cis-BF) were investigated in zebrafish at environmentally relevant concentrations. The addition of Cd, Cu, or Pb significantly increased the mortality of zebrafish in racemate and R-enantiomer of cis-BF–treated groups. In rac-cis-BF– or 1R-cis-BF–treated groups, the addition of Cd, Cu, or Pb caused a decrease in enantiomeric fraction (EF) and an increased ratio of R-enantiomer residues in zebrafish. In 1S-cis-BF–treated groups, coexposure to Cd led to a lower EF and decreased residue levels of S-enantiomer. In addition, coexposure to the 3 metals resulted in different biodegradation characteristics of each enantiomer accompanied with differential changes in the expression of cytochrome P450 (CYP)1, CYP2, and CYP3 genes, which might be responsible for the enantioselective biodegradation of cis-BF in zebrafish. These results suggest that the influence of coexistent metals should be considered in the ecological risk assessment of chiral pyrethroids in aquatic environments. Environ Toxicol Chem 2017;36:2139–2146. © 2017 SETAC
Thermo‐hydrodynamic‐mechanical multiphase flow model for CO2 sequestration in fracturing porous media
Authors: Arzanfudi Mehdi Musivand , Al‐Khoury Rafid
Published: January 2017

In this paper, we introduce a fully coupled thermo‐hydrodynamic‐mechanical computational model for multiphase flow in a deformable porous solid, exhibiting crack propagation due to fluid dynamics, with focus on CO2 geosequestration. The geometry is described by a matrix domain, a fracture domain, and a matrix‐fracture domain. The fluid flow in the matrix domain is governed by Darcy's law and that in the crack is governed by the Navier–Stokes equations. At the matrix‐fracture domain, the fluid flow is governed by a leakage term derived from Darcy's law. Upon crack propagation, the conservation of mass and energy of the crack fluid is constrained by the isentropic process. We utilize the representative elementary volume‐averaging theory to formulate the mathematical model of the porous matrix, and the drift flux model to formulate the fluid dynamics in the fracture. The numerical solution is conducted using a mixed finite element discretization scheme. The standard Galerkin finite element method is utilized to discretize the diffusive dominant field equations, and the extended finite element method is utilized to discretize the crack propagation, and the fluid leakage at the boundaries between layers of different physical properties. A numerical example is given to demonstrate the computational capability of the model. It shows that the model, despite the relatively large number of degrees of freedom of different physical nature per node, is computationally efficient, and geometry and effectively mesh independent. Copyright © 2017 John Wiley & Sons, Ltd.
Geographic heterogeneity in the prevalence of human papillomavirus in head and neck cancer
Authors: Anantharaman Devasena , Abedi‐Ardekani Behnoush , Beachler Daniel C. , Gheit Tarik , Olshan Andrew F. , Wisniewski Kathy , Wunsch‐Filho Victor , Toporcov Tatiana N. , Tajara Eloiza H. , Levi José Eduardo , Moyses Raquel A. , Boccia Stefania , Cadoni Gabriella , Rindi Guido , Ahrens Wolfgang , Merletti Franco , Conway David I. , Wright Sylvia , Carreira Christine , Renard Helene , Chopard Priscilia , McKay‐Chopin Sandrine , Scelo Ghislaine , Tommasino Massimo , Brennan Paul , D'Souza Gypsyamber
Published: January 2017

Human papillomavirus (HPV) causes oropharyngeal squamous cell carcinoma (OPSCC), although strongly divergent results have been reported regarding the prevalence of HPV16 in different countries, whether this represents important differences in etiology remains unclear. Applying rigorous protocols for sample processing, we centrally evaluated 1,420 head and neck tumors (533 oropharynx, 395 oral cavity and 482 larynx) from studies conducted in the US, Europe and Brazil for mucosal HPV DNA and p16INK4a expression to evaluate regional heterogeneity in the proportion of HPV16‐associated OPSCC and other head and neck cancer, and to assess covariates associated with the risk of HPV16‐positive OPSCC. While majority of OPSCC in the US (60%) were HPV16‐positive, this proportion was 31% in Europe and only 4% in Brazil (p < 0.01). Similar differences were observed for other head and neck tumors, ranging from 7% in the US and 5% in Europe, to 0% in South America. The odds of HPV16‐positive OPSCC declined with increasing pack years of smoking (OR: 0.75; 95% CI: 0.64–0.87) and drink years of alcohol use (OR: 0.64; 95% CI: 0.54–0.76). These results suggest that while the contribution of HPV16 is substantial for the oropharynx, it remains limited for oral cavity and laryngeal cancers.
Mechanistic insights on DBU catalyzed β‐amination of nbs to chalcone driving by water: Multiple roles of water
Authors: Yuan Haiyan , Zhang Jingping
Published: January 2017

DFT calculations were conducted to pursue deeper understandings on the mechanism and the explicit role of trace water in the DBU‐catalyzed β‐amination of NBS to chalcone. Being different from previously proposed by Liang et al., a cooperative participation of both DBU and water is noticed in the preferred mechanism. The preferential mechanistic scenario assisted by water undergoes three major steps: the formation of succinimide and HBrO, concerted nucleophilic addition and H‐shift, and keto‐enol tautomerization. Moreover, we found that DBU‐HBrO is unnecessary in the third step and three‐water‐cluster assisted keto‐enol tautomerization is the most advantageous case. It is further noted that the catalytic position of the third water molecule and the proton shift orientation to some extent affect step 3 via O···HO and OH···π interactions, which is confirmed by AIM analysis. The computational results suggest that water molecules play pivotal roles as reactant, catalyst, and stabilizer to promote the reaction of chalcone and NBS. The origin of the more stable transition state structure in the rate‐determining step of DBU‐water catalyzed mechanism is ascribed to noncovalent interactions, halogen bond, and electrostatic interactions than DBU only ones. © 2017 Wiley Periodicals, Inc.
Coordination Behavior of N‐Donor Schiff Base Derived from 2‐Benzoylpyridine Toward Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Pd(II), and Cr(III) Metal Ions: Synthesis, Spectroscopic and Thermal Studies, and Biological Activity
Authors: Emam Sanaa Moustafa , AbouEl‐Enein Saeyda Abou El‐Thana , El‐Seady Safa Mohamed
Published: January 2017

A new Schiff base was prepared from the reaction of 4,4′‐methylenedianiline with 2‐benzoylpyridine in 1:2 molar ratio, as well as its different metal chelates. The structures of the ligand and its metal complexes were studied by elemental analyses, spectroscopic methods (infrared [IR], ultraviolet–visible [UV–vis],
1H nuclear magnetic resonance [NMR], electron spin resonance [ESR]), magnetic moment measurements, and thermal studies. The ligand acts as tetradentate moiety in all complexes. Octahedral geometry was suggested for Mn(II), Cu(II), Cr(III), and Zn(II) chloride complexes and pentacoordinated structure and square planar geometry for Co(II), Ni(II), Cu(NO3
)2, CuBr2
, and Pd(II) complexes. ESR spectra of copper(II) complexes (4)–(6) at room temperature display rhombic symmetry for complex (4) and axial type symmetry for complexes (5) and (6), indicating ground state for Cu(II) complexes. The derivative thermogravimetric (DTG) curves of the ligand and its metal complexes were analyzed by using the rate equation to calculate the thermodynamic and kinetic parameters, which indicated strong binding of the ligand with the metal ion in some complexes. Also, some of these compounds were screened to establish their potential as anticancer agents against the human hepatic cell line Hep‐G2
. The obtained IC50
value of the copper(II) bromide complex (4.34 µg/mL) is the highest among the compounds studied.
Lipid profiling of parkin‐mutant human skin fibroblasts
Authors: Lobasso Simona , Tanzarella Paola , Vergara Daniele , Maffia Michele , Cocco Tiziana , Corcelli Angela
Published: January 2017

Parkin mutations are a major cause of early‐onset Parkinson's disease (PD). The impairment of protein quality control system together with defects in mitochondria and autophagy process are consequences of the lack of parkin, which leads to neurodegeneration. Little is known about the role of lipids in these alterations of cell functions. In the present study, parkin‐mutant human skin primary fibroblasts have been considered as cellular model of PD to investigate on possible lipid alterations associated with the lack of parkin protein. Dermal fibroblasts were obtained from two unrelated PD patients with different parkin mutations and their lipid compositions were compared with that of two control fibroblasts. The lipid extracts of fibroblasts have been analyzed by combined matrix‐assisted laser desorption/ionization‐time‐of‐flight mass spectrometry (MALDI‐TOF/MS) and thin‐layer chromatography (TLC). In parallel, we have performed direct MALDI‐TOF/MS lipid analyses of intact fibroblasts by skipping lipid extraction steps. Results show that the proportions of some phospholipids and glycosphingolipids were altered in the lipid profiles of parkin‐mutant fibroblasts. The detected higher level of gangliosides, phosphatidylinositol, and phosphatidylserine could be linked to dysfunction of autophagy and mitochondrial turnover; in addition, the lysophosphatidylcholine increase could represent the marker of neuroinflammatory state, a well‐known component of PD.
Changes in soil aeration and soil respiration of simulated grave soils after quicklime application
Authors: Mordhorst Anneka , Zimmermann Iris , Fleige Heiner , Horn Rainer
Published: January 2017

The decomposition of buried human remains on cemeteries can be delayed in poorly aerated graves due to high water levels and a low permeable pore system for oxygen and water transport. With aim to improve the soil aeration properties in the burial environment, the addition of quicklime (CaO) to the grave backfill was tested. Quicklime is expected to promote a stronger aggregation and stabilization of the backfilled soil mainly by forcing an immediate dehydration and particle cementation processes.

Two different grave simulations (without buried corpses) were prepared: (1) mixing the grave backfill with 20 kg m−3 quicklime (“CaO”) and (2) backfill without CaO (“NIL”) on a cemetery in Northern Germany. The soil type was a Terric Anthrosol (Stagnic) with a loamy sand texture. Undisturbed soil cores were taken from two depths before and after excavation and backfill at regular intervals of 3 months in order to analyze changes in (1) gaseous transport functions expressed by air‐filled porosity, air permeability (air permeameter), gas diffusivity (double chamber method) and related pore continuity indices as well as in (2) soil respiration (alkali trap method) representing microbial activity.

Results clearly demonstrated a more conductive pore system in the CaO variant reflected by higher gas diffusivity and air permeability over 1 year compared to the NIL variant. Pore continuity indices also indicated a more connective pore system for the CaO variant. Effects of CaO application on soil respiration rate differed between the quarterly sampling times. Results indicated that microorganism were still active under alkaline soil conditions induced by CaO application, but the quantitative determination of biologically produced CO2 is influenced by chemical reactions when hydrated quicklime [Ca(OH)2] was reformed to limestone under consumption of CO2. The experiments indicate that the application of quicklime is a promising approach to improve aeration properties of grave soils and is therefore proposed as an adequate method to improve the aeration of burials on cemeteries.
Upper aerodigestive injuries from detergent ingestion in children
Authors: Sjogren Phayvanh P. , Skarda David E. , Park Albert H.
Published: January 2017

Objectives

To describe the clinical presentations and management of detergent pod ingestion at a tertiary children's hospital.

Study Design

Case series.

Methods

A retrospective chart review of children diagnosed with detergent pod ingestion from June 2010 and March 2015.

Results

Nine cases of detergent pod ingestion were included over a 5‐year period. The average age was 26.3 months (range, 11–43 months). Eight (89%) of the cases were female. The patients had ingested laundry detergent pods (n = 7) and dishwasher detergent pods (n = 2). The majority of patients (67%) had more than one clinical manifestation from ingestion. Presenting symptoms included emesis (78%), respiratory symptoms (56%), throat pain (22%), drooling (33%), and foaming at the mouth (33%). The management of patients depended on the severity of their symptoms and included admission to an overnight observation unit (n = 5), discharge to home directly from the emergency department (n = 2), and admission to the hospital (n = 2). Two (22%) children underwent esophagogastroduodenoscopy. One child (11%) required intubation from bilateral vocal fold immobility.

Conclusion

Injuries to the upper aerodigestive tract after detergent ingestion range from mild gastrointestinal symptoms to respiratory compromise. The majority of children improve with observation alone; however, clinicians should maintain a low threshold for endoscopic evaluation in cases of severe symptoms and airway involvement.

Level of Evidence

4. Laryngoscope, 2016 127:509–512, 2017