bluuebunny/crossref_metadata_2025 huggingface dataset:
Chemical Dynamic Kinetic Resolution and S/R Interconversion of Unprotected α‐Amino Acids
Authors: Takeda Ryosuke , Kawamura Akie , Kawashima Aki , Sato Tatsunori , Moriwaki Hiroki , Izawa Kunisuke , Akaji Kenichi , Wang Shuni , Liu Hong , Aceña José Luis , Soloshonok Vadim A.
Published: September 2014

Reported herein is the first purely chemical method for the dynamic kinetic resolution (DKR) of unprotected racemic α‐amino acids (α‐AAs), a method which can rival the economic efficiency of the enzymatic reactions. The DKR reaction principle can be readily applied for S/R interconversions of α‐AAs, the methodological versatility of which is unmatched by biocatalytic approaches. The presented process features a virtually complete stereochemical outcome, fully recyclable source of chirality, and operationally simple and convenient reaction conditions, thus allowing its ready scalability. A quite unique and novel mode of the thermodynamic control over the stereochemical outcome, including an exciting interplay between axial, helical, and central elements of chirality is proposed.
Wet spun fibers from solutions of cellulose in an ionic liquid with suspended carbon nanoparticles
Authors: Härdelin Linda , Hagström Bengt
Published: September 2014

Wet spun fibers from solutions of dissolving pulp in 1‐ethyl‐3‐methylimidazolium acetate (EmimAc) with up to 50 wt % (based on cellulose) suspended carbon black and graphene nanoplatelets particles were studied. Carbon fillers were dispersed by simple shearing in a Couette type mixer and the resulting spin dope was extruded into a hot water coagulation bath from a single hole spinneret. Microstructure, mechanical properties, and electrical conductivity were assessed as a function of filler loading and discussed in comparison to melt spun fibers with similar fillers. The coagulation process and subsequent drying of wet spun fibers was found to produce a significant microporosity, more so the higher the filler loading. The electrical percolation threshold was quite high in the wet spun fibers and relatively modest values of conductivity were obtained with regard to the high filler loadings. Carbon black was found to be superior to graphene nanoplatelets. This was related to flow‐induced orientation effects. The mechanical properties of the carbon‐filled fibers were found to be similar or lower compared to the pure cellulose fibers because of low interfacial interactions and formation of microporosity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41417.
From Spaghetti Bowl to Jigsaw Puzzle? Fixing the Mess in Regional and Global Trade
Authors: Menon Jayant
Published: September 2014

The rise of mega‐regionals such as theRegionalComprehensiveEconomicPartnership (RCEP) and theTrans‐PacificPartnership (TPP) suggests that the world trade system is fragmenting and appears more like a jigsaw puzzle than a spaghetti bowl. There are both regional and global jigsaw puzzles to be solved—in that order—to clean up the world trade system. But is this even likely? The difficulties of free trade agreement (FTAA) consolidation at the regional level are well known, while piecing together the blocs around the world to form a coherent whole is even more challenging. In this context, a way forward is to return to the most widely used modality of trade liberalisation—unilateral actions—but this time involving the multilateralisation of preferences rather than unreciprocated reductions in tariff rates. Multilateralisation of preferences presents a practical way forward in addressing the disarray in the world trade system.
NiII Metalations of [40]‐ and [42]Nonaphyrins(1.1.1.1.1.1.1.1.1): The Largest Doubly Twisted Hückel Antiaromatic Molecule
Authors: Soya Takanori , Naoda Koji , Osuka Atsuhiro
Published: September 2014

NiII metalation of [42]nonaphyrin gave two Hückel aromatic [42]nonaphyrin NiII complexes that possess different doubly twisted figure‐eight conformations. While these complexes are conformers, the activation barriers for conformational interconversion were found to be exceptionally high. However, one‐way isomerization from the higher‐energy conformer to the lower‐energy conformer can be induced upon treatment with trifluoroacetic acid (TFA). This conformational isomerization has been suggested to proceed via a protonation‐induced caterpillar‐like conformational rotation of the metal‐free hexaphyrin‐like segment by examining the similar isomerization of an A3B6‐type [42]nonaphyrin NiII complex. RhI metalation of the lower‐energy [42]nonaphyrin NiII complex afforded a [42]nonaphyrin NiII‐RhI hybrid complex, which was oxidized with p‐chloranil to produce a [40]nonaphyrin NiII‐RhI hybrid complex as the largest doubly twisted Hückel antiaromatic molecule to date.
Proton Transfer versus Hydrogen Bonding: The Reduction of Ubiquinone Q2 Incorporated in a Self‐Assembled Monolayer in Unbuffered Aqueous Solution
Authors: Liehn Cédric , Bouvet Marcel , Meunier‐Prest Rita
Published: September 2014

The electrochemical reduction of ubiquinone Q2 (UQ2) in unbuffered aqueous media was investigated over a pH range of 2 to 11, and the results were compared to those obtained in our previous work in buffered solutions. The short isoprene chains of UQ2 were incorporated in a self‐assembled monolayer. Analysis of the mechanism and a study in D2O solutions allowed us to demonstrate the important role of hydrogen bonding in the stabilization of the reduced species, also in water. If the concentration of H+ is low relative to that of the quinone, the electrochemical reaction does not proceed through proton‐coupled electron transfer, as it does in buffered medium or at low pH values (pH<4.4). We proved that the reduction of UQ2 is a two‐electron process followed by a first‐order reaction. Unlike that observed for most quinones in unbuffered media, UQ2 used the labile hydrogen of the isoprene chain to compensate for the lack of protons through a tautomeric reaction.
Out‐of‐Cell Oxygen Diffusivity Evaluation in Lithium–Air Batteries
Authors: He Weidong , Wang Xiaoning , Ye Luhan , Pan Yu , Song Yuanqiang , Liu Aifang , Wang Wei , Zhang Hongping , Qi Hongxue , Zhou Ming , Wang Zhiguo , Zhang Kelvin H. L. , Dickerson James H.
Published: September 2014

The diffusion rate of oxygen has a significant impact on the power density, rate capacity, discharge capacity, and electrolyte stability of lithium–air batteries (H.‐G. Jung, J. Hassoun, J.‐B. Park, Y.‐K. Sun, B. Scrosati, Nat. Chem. 2012, 4, 579–585; J. Read, K. Mutolo, M. Ervin, W. Behl, J. Wolfenstine, A. Driedger, D. Foster, J. Electrochem. Soc.­ 2003, 150, A1351–A1356; Y. Cui, Z. Wen, X. Liang, Y. Lu, J. Jin, M. Wu, X. Wu, Energy Environ. Sci.­ 2012, 5, 7893–7897). Oxygen diffusivity in the solid porous cathodes of gas‐based batteries is typically obtained by employing a few electrochemical models. In addition to the indirect computing characteristic, previous methods of evaluating oxygen diffusivity require multiple voltage–current experiments over intact lithium–air batteries, and can cause unnecessary costs resulting from the waste of materials from other battery components (J. Read, J. Electrochem. Soc. 2006, 153, A96–A100). In this report, through derivation and analytical design, a methodology is proposed for the direct out‐of‐cell oxygen diffusivity measurement in lithium–air batteries. The proposed electrochemical devices allow for efficient diffusivity measurements in porous solid cathodes, as well as subsequent quantitative pre‐evaluation of important battery parameters including electrode porosity, thickness, and tortuosity. The proposed methodology is expected to facilitate the development of low‐cost battery systems for a variety of applications, such as large‐capacity automobile batteries and electronics.
Chemical Optimization for Simultaneous Voltammetric Detection of Molybdenum and Silver Nanoparticles in Aqueous Buffer Solutions
Authors: Goda Tatsuro , Oohashi Mikiya , Matsumoto Akira , Hoshi Toru , Sawaguchi Takashi , Pumera Martin , Miyahara Yuji
Published: September 2014

Simultaneous acquisition of redox signals from different types of metal nanoparticles (NPs) in a multiplexing system requires a good separation in redox potential from each component for successful identification. The appearance of a single distinct peak for each NP type is also preferred. Here, we report variations in the electrochemical nature of molybdenum (Mo) and silver (Ag) NPs cast on a glassy carbon electrode that are sensitive to various conditions of the measurement solution, such as buffering capacity and electrolyte concentration. A series of experiments allowed us to find optimal conditions, where Mo NPs showed a single oxidation peak with good separation of the redox potential from that of Ag NPs (ΔE≈0.25 V), by using differential‐pulse voltammetry (DPV). In the simultaneous monitoring of Mo and Ag NPs under the optimal conditions, the peak currents in DPV were quantitative for the amount of Mo/Ag NPs ranging from 7.8/20 to 500/20 ng ng−1 and from 500/20 to 500/0.31 ng ng−1.
Three‐Way Cooperativity in d8 Metal Complexes with Ligands Displaying Chemical and Redox Non‐Innocence
Authors: Deibel Naina , Hohloch Stephan , Schweinfurth David , Weisser Fritz , Grupp Anita , Sarkar Biprajit
Published: September 2014

Reversible proton‐ and electron‐transfer steps are crucial for various chemical transformations. The electron‐reservoir behavior of redox non‐innocent ligands and the proton‐reservoir behavior of chemically non‐innocent ligands can be cooperatively utilized for substrate bond activation. Although site‐decoupled proton‐ and electron‐transfer steps are often found in enzymatic systems, generating model metal complexes with these properties remains challenging. To tackle this issue, we present herein complexes [(cod−H)M(μ‐L2−) M(cod−H)] (M=PtII, [1] or PdII, [2], cod=1,5‐cyclooctadiene, H2L=2,5‐di‐[2,6‐(diisopropyl)anilino]‐1,4‐benzoquinone), in which cod acts as a proton reservoir, and L2− as an electron reservoir. Protonation of [2] leads to an unusual tetranuclear complex. However, [1] can be stepwise reversibly protonated with up to two protons on the cod−H ligands, and the protonated forms can be stepwise reversibly reduced with up to two electrons on the L2− ligand. The doubly protonated form of [1] is also shown to react with OMe− leading to an activation of the cod ligands. The site‐decoupled proton and electron reservoir sources work in tandem in a three‐way cooperative process that results in the transfer of two electrons and two protons to a substrate leading to its double reduction and protonation. These results will possibly provide new insights into developing catalysts for multiple proton‐ and electron‐transfer reactions by using metal complexes of non‐innocent ligands.
Nef Reaction with Molecular Oxygen in the Absence of Metal Additives, and Mechanistic Insights
Authors: Umemiya Shigenobu , Nishino Kentaro , Sato Itaru , Hayashi Yujiro
Published: September 2014

A Nef reaction has been developed that is conducted under mildly basic conditions with molecular oxygen as an oxidant, without the need for metal additives. Whereas nitroalkanes are converted into ketones in good yield, nitroalkenes are transformed into α,β‐unsaturated ketones in one‐pot by double‐bond isomerization followed by the oxygen‐mediated Nef reaction. The reaction protocol is both mild and general, and tolerates acid‐ and base‐labile functionality or protecting groups. When oxygen‐saturated solvents are employed, the reaction completes within 20 min. Mechanistically, the addition of nitronate ion and molecular oxygen is proposed to proceed initially through a single‐electron transfer event, as indicated by radical clock experiments. This ultimately generates a putative 1,1‐dioxirane, which reacts further with another nitronate ion to generate the ketone. Involvement of a 1,1‐dioxirane is supported by intramolecular trapping experiments with sulfide at the γ‐position of the nitro‐moiety.
Receptor‐Bound Conformation of Cilengitide Better Represented by Its Solution‐State Structure than the Solid‐State Structure
Authors: Marelli Udaya Kiran , Frank Andreas O. , Wahl Bernhard , La Pietra Valeria , Novellino Ettore , Marinelli Luciana , Herdtweck Eberhardt , Groll Michael , Kessler Horst
Published: September 2014

The X‐ray crystal and NMR spectroscopic structures of the peptide drug candidate Cilengitide (cyclo(RGDf(NMe)Val)) in various solvents are obtained and compared in addition to the integrin receptor bound conformation. The NMR‐based solution structures exhibit conformations closely resembling the X‐ray structure of Cilengitide bound to the head group of integrin αvβ3. In contrast, the structure of pure Cilengitide recrystallized from methanol reveals a different conformation controlled by the lattice forces of the crystal packing. Molecular modeling studies of the various ligand structures docked to the αvβ3 integrin revealed that utilization of the solid‐state conformation of Cilengitide leads—unlike the solution‐based structures—to a mismatch of the ligand–receptor interactions compared with the experimentally determined structure of the protein–ligand complex. Such discrepancies between solution and crystal conformations of ligands can be misleading during the structure‐based lead optimization process and should thus be taken carefully into account in ligand orientated drug design.
Strain and factor selection for carbon dioxide fixation using microalgae cultivated in oil sands process water
Authors: Kasiri Sepideh , Prasad Vinay , Ulrich Ania
Published: September 2014

Biological fixation of CO2 using microalgae is a potential CO2 reduction strategy which can be applied to the oil sands operations in Alberta. These operations also produce large amounts of oil sands process water (OSPW), which can act as a growth medium for the microalgae. In this study, three different microalgae: Botryococcus braunii, Chlorella pyrenoidosa and Chlorella kessleri were investigated for their ability to grow in OSPW, and to uptake CO2. Also, the effect of phosphate, nitrate, CO2 concentrations and light intensity were studied using a fractional two‐level and a full two‐level factorial design. These investigations eliminated Botryococcus braunii as it cannot grow in OSPW, and demonstrated that Chlorella kessleri has a higher CO2 uptake rate than Chlorella pyrenoidosa. Moreover, CO2 concentration, light intensity and phosphate concentration proved to have the strongest effects (in that order) on the growth and CO2 uptake rate of Chlorella kessleri.
Electronic cigarette use among patients with cancer: Characteristics of electronic cigarette users and their smoking cessation outcomes
Authors: Borderud Sarah P. , Li Yuelin , Burkhalter Jack E. , Sheffer Christine E. , Ostroff Jamie S.
Published: September 2014

BACKGROUND

Given that continued smoking after a cancer diagnosis increases the risk of adverse health outcomes, patients with cancer are strongly advised to quit. Despite a current lack of evidence regarding their safety and effectiveness as a cessation tool, electronic cigarettes (E‐cigarettes) are becoming increasingly popular. To guide oncologists' communication with their patients about E‐cigarette use, this article provides what to the authors' knowledge is the first published clinical data regarding E‐cigarette use and cessation outcomes among patients with cancer.

METHODS

A total of 1074 participants included smokers (patients with cancer) who recently enrolled in a tobacco treatment program at a comprehensive cancer center. Standard demographic, tobacco use history, and follow‐up cessation outcomes were assessed.

RESULTS

A 3‐fold increase in E‐cigarette use was observed from 2012 to 2013 (10.6% vs 38.5%). E‐cigarette users were more nicotine dependent than nonusers, had more prior quit attempts, and were more likely to be diagnosed with thoracic and head or neck cancers. Using a complete case analysis, E‐cigarette users were as likely to be smoking at the time of follow‐up as nonusers (odds ratio, 1.0; 95% confidence interval, 0.5‐1.7). Using an intention‐to‐treat analysis, E‐cigarette users were twice as likely to be smoking at the time of follow‐up as nonusers (odds ratio, 2.0; 95% confidence interval, 1.2‐3.3).

CONCLUSIONS

The high rate of E‐cigarette use observed is consistent with recent articles highlighting increased E‐cigarette use in the general population. The current longitudinal findings raise doubts concerning the usefulness of E‐cigarettes for facilitating smoking cessation among patients with cancer. Further research is needed to evaluate the safety and efficacy of E‐cigarettes as a cessation treatment for patients with cancer. Cancer 2014;120:3527–3535. © 2014 American Cancer Society.
Ultrafast Twisting Dynamics of Thioflavin‐T: Spectroscopy of the Twisted Intramolecular Charge‐Transfer State
Authors: Ghosh Rajib , Palit Dipak K.
Published: September 2014

Understanding the excited‐state properties of thioflavin‐T (ThT) has been of immense importance, because of its efficient amyloid‐sensing ability related to neurodegenerative disorders. The excited‐state dynamics of ThT is studied by using sub‐pico‐ and nanosecond time‐resolved transient absorption techniques as well as density functional theory (DFT)/time‐dependent DFT calculations. Barrierless twisting around the central CC bond between two aromatic moieties is the dominant process that contributes to the ultrafast dynamics of the S1 state. The spectroscopic properties of the intramolecular charge‐transfer state are characterized for the first time. The energetics of the S0 and S1 states has also been correlated with the experimentally observed spectroscopic parameters and structural dynamics. A longer‐lived transient state populated with a very low yield has been characterized as the triplet state.
Assembling Mixed Carboxylic Acid Molecules on Hierarchical Structured Aluminum Substrates for the Fabrication of Superoleophobic Surfaces with Controlled Oil Adhesion
Authors: Cheng Zhongjun , Lai Hua , Du Ying , Hou Rui , Li Chong , Zhang Naiqing , Sun Kening
Published: September 2014

Controlling oil adhesion on the superoleophobic surfaces is very important in both fundamental research and practical applications. Herein, we report a new method through modification of mixed carboxylic acid (CH3(CH2)6COOH and CF3(CF2)6COOH) molecules on hierarchical structured aluminum substrates toward the fabrication of superoleophobic surfaces with tunable adhesion. The oil adhesion can be controlled by changing the concentration of CF3(CF2)6COOH (xF) in the modified solution. Detailed research indicates that the tunable effect is ascribed to the combined effect of the surface chemistry variation and the hierarchical structures on the substrates. Furthermore, we also demonstrate an application of our surfaces in a droplet‐based microreactor. The results reported here can not only provide a new idea for fabrication of superoleophobic surfaces with tunable adhesion but can also potentially be used in many applications, such as microfluidic devices and chemical microreactors.
Use of Bipolar Membranes for Maintaining Steady‐State pH Gradients in Membrane‐Supported, Solar‐Driven Water Splitting
Authors: McDonald Michael B. , Ardo Shane , Lewis Nathan S. , Freund Michael S.
Published: September 2014

A bipolar membrane can maintain a steady‐state pH difference between the sites of oxidation and reduction in membrane‐supported, solar‐driven water‐splitting systems without changing the overall thermodynamics required to split water. A commercially available bipolar membrane that can serve this purpose has been identified, its performance has been evaluated quantitatively, and is demonstrated to meet the requirements for this application. For effective utilization in integrated solar‐driven water‐splitting systems, such bipolar membranes must, however, be modified to simultaneously optimize their physical properties such as optical transparency, electronic conductivity and kinetics of water dissociation.
Phase noise characterization of oscillators through Ito calculus
Authors: Jahanbakht Sajad , Farzaneh Forouhar
Published: September 2014

Recent phase noise analysis techniques of oscillators mainly rely on solving a stochastic differential equation governing the phase noise process. This equation has been solved in the literature using a number of mathematical tools from probability theory like deriving the Fokker–Planck equation governing the phase noise probability density function. Here, a completely different approach for solving this equation in presence of white noise sources is introduced that is based on the Ito calculus for stochastic differential equations. Time‐domain analytical expressions for the correlation of the noisy variables of the oscillator are derived that in asymptotically large times give the steady‐state stochastic correlations as well as the power spectral densities of the variables. The validity of the new approach is verified by comparing its results against extensive Monte‐Carlo simulations. This approach is applied to an oscillator with a dielectric resonator at 4.127 GHz, and a very good agreement between its results with those of the Monte‐Carlo simulations and the previous approaches is observed. Copyright © 2014 John Wiley & Sons, Ltd.
Synthesis and α‐Glucosidase and α‐Amylase Inhibitory Activity Evaluation of Azido‐ and Aminocyclitols
Authors: Aydin Gökay , Ally Khamis , Aktaş Fatih , Şahin Ertan , Baran Arif , Balci Metin
Published: September 2014

For the synthesis of some azido‐ and aminocyclitols, (3aRS,7aSR)‐1,3,3a,7a‐tetrahydroisobenzofuran was used as the starting material. For further functionalization of the diene unit, the diene was subjected to epoxidation reactions to give mono‐ and bisepoxides depending on the amount of m‐chloroperbenzoic acid used. The ring‐opening of the epoxide functionality with NaN3 resulted in the formation of mono‐ and bisazido cyclitols. The tetrahydrofuran ring was opened in an acid‐catalysed reaction with sulfamic acid. The reduction of azide groups to give amines provided various amino‐ and bisaminocyclitol derivatives. The inhibitory effects of 20 compounds against α‐glucosidase and α‐amylase were tested. The results indicated that some of these compounds seem to have good inhibitory activity against α‐glucosidase, and low inhibitory activity against α‐amylase. Furthermore, it was demonstrated that the number and position of azides, amines, and hydroxy groups appeared to play an important role in determining the inhibitory potency of these compounds.
Synthesis of 2‐Substituted 1,3‐Benzoselenazoles from Carboxylic Acids Promoted by Tributylphosphine
Authors: Schwartz Radatz Cátia , Rampon Daniel S. , Balaguez Renata A. , Alves Diego , Schneider Paulo Henrique
Published: September 2014

We report a general, practical, and simple metal‐free method for the synthesis of 2‐substituted 1,3‐benzoselenazoles by the reaction of bis(2‐aminophenyl)diselenide with a wide range of carboxylic acids, promoted by tributylphosphine. This efficient reaction furnishes 2‐aryl‐1,3‐benzoselenazoles in good yields and tolerates a variety of substituents at the aryl moiety of carboxylic acids. For the first time, 2‐alkyl‐1,3‐benzoselenazoles could be obtained from aliphatic carboxylic acids and thiazolidine‐4‐carboxylic acid in high chemical yields. The use of focused microwave irradiation considerably decreased the reaction time from 48 to 2 h. The experimental data provide insights into the mechanism of the reaction.
Efficient Regioselective Synthesis of 3,4,5‐Trisubstituted 1,2,4‐Triazoles on the Basis of a Lithiation–Trapping Sequence
Authors: Mansueto Rosmara , Perna Filippo Maria , Salomone Antonio , Perrone Serena , Florio Saverio , Capriati Vito
Published: September 2014

The presence of an electron‐donating methoxy group at the 4′‐position of 4‐phenyl‐3,5‐dimethyl‐1,2,4‐triazole is beneficial to lateral metalation/functionalization of this ring system once sBuLi is employed as the base and THF is used as the solvent at –78 °C; this opens up an alternative approach towards the synthesis of several 1,2,4‐triazole derivatives. Both carbon‐ and heteroatom‐based halides are competent electrophiles for this transformation, as are aliphatic and aromatic aldehydes and ketones, isocyanates, carboxylic acid derivatives, and α,β‐unsaturated carbonyl compounds. The easy elaboration of such a group to phenol derivatives also provides greater flexibility in synthetic design.
Genotoxicity of 1‐methylpyrene and 1‐hydroxymethylpyrene in chinese hamster V79‐derived cells expressing both human CYP2E1 and SULT1A1
Authors: Jiang Hao , Lai Yanmei , Hu Keqi , Chen Danxun , Liu Bixuan , Liu Yungang
Published: September 2014

1‐Methylpyrene (1‐MP) is a widespread pollutant that is carcinogenic in animals following metabolic activation. Previous studies have shown that benzylic hydroxylation of 1‐MP, catalyzed by multiple CYP isoforms, gives rise to 1‐hydroxymethylpyrene (1‐HMP), which becomes bioreactive following further metabolism by various sulfotransferase (SULT) isoforms. However, the mutagenic and chromosome damaging effects of 1‐MP and 1‐HMP in mammalian cells have not been investigated. In this study a Chinese hamster V79‐derived cell line expressing both human CYP2E1 and human SULT1A1 was used to investigate the ability of 1‐MP and 1‐HMP to induce cytotoxicity (using the CCK‐8 assay), micronuclei and Hprt gene mutations. The role of each enzyme was investigated through co‐exposure in the presence of an enzyme inhibitor. We found that at concentrations of 0.5–4 μM and 5–20 μM, under conditions where no reduction in cell viability/growth occurred, 1‐HMP and 1‐MP induced micronuclei in V79‐hCYP2E1‐hSULT1A1 cells in a concentration‐dependent manner; however, both compounds were inactive in V79 cells. Similarly, they both caused an increase in Hprt mutant frequency in V79‐hCYP2E1‐hSULT1A1 cells in these concentration ranges, with 1‐MP impairing cell viability/growth at 10 μM and above in the mutagenicity assay. The compounds were again both inactive in V79 cells. The effects of 1‐HMP in V79‐hCYP2E1‐hSULT1A1 cells were blocked or reduced by addition of pentachlorophenol (PCP), a SULT1 inhibitor; the genotoxicity of 1‐MP was significantly reduced by either 1‐aminobenotrazole, a CYP2E1 inhibitor, or PCP. The results suggest that human CYP2E1 and SULT1A1 cooperate to activate 1‐MP and cause genotoxicity in mammalian cells. Environ. Mol. Mutagen. 56:404–411, 2015. © 2014 Wiley Periodicals, Inc.
EPA May Go Beyond Law and Science in Setting NAAQS
Authors: Fraiser Lucy
Published: September 2014

Information from highly respected sources, such as the American Cancer Society, indicates that only about 2 percent of cancer deaths in the United States are the result of exposures to carcinogenic agents in the workplace, community, and other settings. But the news about health risks from environmental exposures to air pollutants is almost constant. Although the US air quality has improved dramatically in the last 30 years, each recent review of a National Ambient Air Quality Standard (NAAQS) by the US Environmental Protection Agency (EPA) has resulted in a reduction in existing standards or replacement by a completely different and generally more stringent standard.
Economics: Latest FERC Outlook Showed Adequate Capacity, Enhanced Transmission, Higher Prices
Authors:   FERC Staff
Published: September 2014

Electric and natural gas market conditions this summer will reflect exceptional gas burn and storage withdrawals this winter, and the anticipation of a warmer‐than‐normal summer for much of the country. The possibility of a summer El Niño may moderate temperatures and associated market impacts. California Independent System Operator (CAISO) markets face a deep drought, while market expansions in the Southwest Power Pool (SPP) and Midcontinent Independent System Operator (MISO) enter their first summer period of operation.
Electric Regulation: Gas Prices Affect Electricity Costs Most Strongly in Northeast and Mid‐Atlantic
Authors: Bowden Nicholas S.
Published: September 2014

The US Energy Information Administration (EIA) began the public posting of select regional electricity and natural gas hub prices in concert with the Federal Energy Regulatory Commission's (FERC's) proposal to change the scheduling and operating practices used by interstate pipelines. This data includes eight corresponding electricity and natural gas trading hubs.
Application of benchmark dose modeling to protein expression data in the development and analysis of mode of action/adverse outcome pathways for testicular toxicity
Authors: Chepelev Nikolai L. , Meek M. E. (Bette) , Yauk Carole Lyn
Published: September 2014

Reliable quantification of gene and protein expression has potential to contribute significantly to the characterization of hypothesized modes of action (MOA) or adverse outcome pathways for critical effects of toxicants. Quantitative analysis of gene expression by benchmark dose (BMD) modeling has been facilitated by the development of effective software tools. In contrast, protein expression is still generally quantified by a less robust effect level (no or lowest [adverse] effect levels) approach, which minimizes its potential utility in the consideration of dose–response and temporal concordance for key events in hypothesized MOAs. BMD modeling is applied here to toxicological data on testicular toxicity to investigate its potential utility in analyzing protein expression relevant to the proposed MOA to inform human health risk assessment. The results illustrate how the BMD analysis of protein expression in animal tissues in response to toxicant exposure: (1) complements other toxicity data, and (2) contributes to consideration of the empirical concordance of dose–response relationships, as part of the weight of evidence for hypothesized MOAs to facilitate consideration and application in regulatory risk assessment. Lack of BMD analysis in proteomics has likely limited its use for these purposes. This paper illustrates the added value of BMD modeling to support and strengthen hypothetical MOAs as a basis to facilitate the translation and uptake of the results of proteomic research into risk assessment. Copyright © 2014 Her Majesty the Queen in Right of Canada. Journal of Applied Toxicology © 2014 John Wiley & Sons, Ltd.
Melatonin and clonidine premedication has similar impact on the pharmacokinetics and pharmacodynamics of propofol target controlled‐infusions
Authors: Bienert Agnieszka , Wawrzyniak Katarzyna , Wiczling Paweł , Przybyłowski Krzysztof , Kokot Zenon J. , Matysiak Jan , Pachutko Agnieszka , Józefowicz Martyna , Kusza Krzysztof , Grześkowiak Edmund
Published: September 2014

Recently oral melatonin has been proposed as an agent for premedication. In this study, we compared melatonin with clonidine, considering its anxiolytic properties as well as the influence of both agents on the pharmacokinetic, hypnotic, and hemodynamic effects of propofol during propofol–remifentanil total intravenous anesthesia (TIVA). The dataset under analysis included 32 patients scheduled for a functional endoscopic sinus surgery. The population pharmacokinetic modeling was done with NONMEM. The PK of propofol was described with a two‐compartment disposition model, whereas the BIS and AAI were described with a sigmoidal Emax model linked with the propofol concentration via the biophase compartment. The anxiolytic effect was assessed by means of the visual analog scale for anxiety (VAS‐A). The population PK/PD model was successfully developed to describe the data. No significant differences in the PK/PD of propofol were noted due to the premedication with clonidine and melatonin. Melatonin was less effective than clonidine in reducing patients' anxiety at the induction of anesthesia, whereas clonidine premedication was associated with greater decrease in heart rate and blood pressure. A decreased EC50 (2.47 vs. 3.17 mg/L) and increased slope (2.71 vs. 1.30) of the sigmoidal Emax relationship was observed for the AAI index, as compared with the BIS measurements.
Outcomes in biliary malignancy
Authors: Groot Koerkamp Bas , Fong Yuman
Published: September 2014

The biliary malignancies that are reviewed here are gallbladder cancer (GBC), intrahepatic cholangiocarcinoma (IHC), and perihilar cholangiocarcinoma (PHC). The focus is on outcomes after potentially curative resection of biliary malignancies. Key outcomes are postoperative mortality, median and 5‐year overall survival (OS), recurrence‐free survival, and recurrence patterns. Poor prognostic factors for recurrence and survival as well as prognostic models are also discussed. The incidence of biliary malignancies in the United States is about 5 in 100,000. Postoperative mortality for resection of GBC and IHC is similar to that of liver resections for other indications. However, 90 day postoperative mortality after liver resection for PHC is about 10%. For GBC, median OS depends strongly on the T‐stage and ranges from 8 months (pT3) to 79 months (pT1b). Median OS after resection for IHC is about 30 months, and for PHC about 38 months. The majority of patients with biliary malignancies develop a recurrence after resection. Patients with GBC recur early with a median time to recurrence of 12 months, versus about 20 months for IHC and PHC. In patients with resected IHC or PHC locoregional recurrence was the only site of recurrence in about 60% of patients, versus 15% in patients with GBC. Poor prognostic factors after resection of all biliary malignancies include the presence of lymph node metastasis, a positive surgical resection margin, and moderate or poor tumor differentiation. Several prognostic nomograms have been developed to predict long‐term outcomes of biliary cancer resection. J. Surg. Oncol. 2014 110:585–591. © 2014 Wiley Periodicals, Inc.
Study of Fuchsin Acid Fading in Micellar Media
Authors: SAMIEY B. , DALVAND Z.
Published: September 2014

The rate constant of alkaline fading of fuchsin acid (FA2−) was measured in the presence of nonionic (TX‐100), cationic (dodecltrimethylammonium bromide, DTAB), and anionic (sodium dodecyl sulfate, SDS) surfactants. FA2− has three negatively charged substituents and one positive charge, and this makes the behavior of FA2– different from dyes such as bromophenol blue. It was observed that the reaction rate constant decreased in the presence of TX‐100, DTAB, and SDS. Binding constants of FA2− to TX‐100, DTAB, and SDS and the related thermodynamic parameters were calculated by the stoichiometric (classical) model. The results show that the binding of FA2− to SDS is endothermic in both regions, and the binding of FA2− to DTAB and TX‐100 is exothermic in one region and endothermic in another region of the used concentration range of these surfactants. Also, the binding constants of FA2− to surfactant molecules of SDS/TX‐100 and DTAB/TX‐100 mixed micelles were obtained.
Mechanically Tailored Agarose Hydrogels through Molecular Alloying withβ‐Sheet Polysaccharides
Authors: Forget Aurelien , Pique Raphaelle‐Anne , Ahmadi Vincent , Lüdeke Steffen , Shastri V. Prasad
Published: September 2014

There is mounting evidence that the mechanical property of tissues provides important cues that control cell fate. However, implementation of hydrogels with tunable physicochemical properties is limited due to the challenges associated with crosslinking chemistries. It has been recently shown that mechanically well‐defined injectable polysaccharide hydrogels can be engineered by switching their secondary structure from an α‐helix to a β‐sheet. Based on these findings, a new concept is presented to tailor the mechanical properties of agarose hydrogels via the blending with the β‐sheet‐rich carboxylated derivative. Using this simple strategy, gels with predictable roughness, fiber organization, and shear modulus ranging from 0.1 to 100 kPa can be formulated. Hydrogels whose mechanical properties can be precisely tailored in vivo without the recourse for chemical reactions are expected to play an important role in implementing mechanobiology paradigms inde novotissue engineering.

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Utilizing Stretch‐Tunable Thermochromic Elastomeric Opal Films as Novel Reversible Switchable Photonic Materials
Authors: Schäfer Christian G. , Lederle Christina , Zentel Kristina , Stühn Bernd , Gallei Markus
Published: September 2014

In this work, the preparation of highly thermoresponsive and fully reversible stretch‐tunable elastomeric opal films featuring switchable structural colors is reported. Novel particle architectures based on poly(diethylene glycol methylether methacrylate‐co‐ethyl acrylate) (PDEGMEMA‐co‐PEA) as shell polymer are synthesized via seeded and stepwise emulsion polymerization protocols. The use of DEGMEMA as comonomer and herein established synthetic strategies leads to monodisperse soft shell particles, which can be directly processed to opal films by using the feasible melt‐shear organization technique. Subsequent UV crosslinking strategies open access to mechanically stable and homogeneous elastomeric opal films. The structural colors of the opal films feature mechano‐ and thermoresponsiveness, which is found to be fully reversible. Optical characterization shows that the combination of both stimuli provokes a photonic bandgap shift of more than 50 nm from 560 nm in the stretched state to 611 nm in the fully swollen state. In addition, versatile colorful patterns onto the colloidal crystal structure are produced by spatial UV‐induced crosslinking by using a photomask. This facile approach enables the generation of spatially cross‐linked switchable opal films with fascinating optical properties. Herein described strategies for the preparation of PDEGMEMA‐containing colloidal architectures, application of the melt‐shear ordering technique, and patterned crosslinking of the final opal films open access to novel stimuli‐responsive colloidal crystal films, which are expected to be promising materials in the field of security and sensing applications.

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(+)‐Catechin ameliorates diabetic nephropathy by trapping methylglyoxal in type 2 diabetic mice
Authors: Zhu Dina , Wang Lei , Zhou Qile , Yan Shijun , Li Zhi , Sheng Jun , Zhang Wensheng
Published: September 2014

Scope

Accumulation of glycolytic metabolite methylglyoxal (MG) in diabetic kidney is thought to contribute to the pathogenesis of nephropathy, either as a direct toxin or as a precursor for advanced glycation end products (AGEs). Using (+)‐catechin (CE), a novel MG trapper, we investigated whether MG trapping is sufficient to prevent the progression of diabetic nephropathy in type 2 diabetic mice.

Methods and results

CE markedly trapped exogenous MG in a time‐ and dose‐dependent manner and formed mono‐MG‐CE and di‐MG‐CE adducts, which were characterized by HPLC‐ESI‐Q‐TOFMS. In vivo, CE administration for 16 wk significantly ameliorated renal dysfunction in type 2 diabetic db/db mice, partially due to MG trapping, which in turn inhibited AGEs formation and lowered proinflammatory cytokines, including tumor necrosis factor α and IL‐1β. Similarly, the MG trapping and cellular signaling inhibition effects of CE were observed in human endothelium‐derived cells under high glucose conditions.

Conclusion

CE might ameliorate renal dysfunction in diabetic mice as consequences of inhibiting AGEs formation and cutting off inflammatory pathway via MG trapping. Thus, CE may be a potential natural product as an MG scavenger against diabetes‐related complications.
Measurement of post‐void residual urine
Authors: Asimakopoulos Anastasios D. , De Nunzio Cosimo , Kocjancic Ervin , Tubaro Andrea , Rosier Peter F. , Finazzi‐Agrò Enrico
Published: September 2014

Aims

To present the teaching module “Measurement of Post‐void residual urine.”

Methods

This module has been prepared by a Working Group of the ICS Urodynamics Committee. The methodology used included comprehensive literature review, consensus formation by the members of the Working Group, and review by members of the ICS Urodynamics Committee core panel.

Results

In this ICS teaching module the evidence for and relevance of PVR measurement in patients with lower urinary tract dysfunction (LUTD) is summarized; in short: The interval between voiding and post‐void residual (PVR) measurement should be of short duration and ultrasound bladder volume measurement is preferred to urethral catheterization. There is no universally accepted definition of a significant residual urine volume. Large PVR (>200–300 ml) may indicate marked bladder dysfunction and may predispose to unsatisfactory treatment results if for example, invasive treatment for bladder outlet obstruction (BOO) is undertaken. PVR does not seem to be a strong predictor of acute urinary retention and does not indicate presence of BOO specifically. Although the evidence base is limited, guidelines on assessment of LUTS generally include PVR measurement.

Conclusion

Measurement of PVR is recommended in guidelines and recommendations on the management of LUTS and urinary incontinence, but the level of evidence for this measurement is not high. This manuscript summarizes the evidence and provides practice recommendations for teaching purposes in the framework of an ICS teaching module. Neurourol. Urodynam. 35:55–57, 2016. © 2014 Wiley Periodicals, Inc.
Health nonprofits online: the use of frames and stewardship strategies to increase stakeholder involvement
Authors: Patel Sheetal J. , Weberling McKeever Brooke
Published: September 2014

This study examines connections between the conceptual frameworks of compassion fatigue (burnout toward social issues) and related stewardship strategies that are used as a form of best practices to address the issue of compassion fatigue. A content analysis of 117 health nonprofit websites (457 web pages) investigates how nonprofit health organization websites are framing their communication to various stakeholders and how the strategies of stewardship are employed online. Findings indicate that although health nonprofits are using positive frames and multiple stewardship strategies, more could be done by nonprofit marketing practitioners to facilitate positive, long‐term relationships with stakeholders in an environment of increased communication and compassion fatigue.

Copyright © 2014 John Wiley & Sons, Ltd.
Comparison between piperacillin/tazobactam and cefepime monotherapies as an empirical therapy for febrile neutropenia in children with hematological and malignant disorders: A prospective, randomized study
Authors: Sano Hirozumi , Kobayashi Ryoji , Suzuki Daisuke , Kishimoto Kenji , Yasuda Kazue , Kobayashi Kunihiko
Published: September 2014

To evaluate the efficacy and safety of piperacillin/tazobactam (PIPC/TAZ) or cefepime (CFPM) monotherapy for febrile neutropenia (FN) in children, a total of 53 patients with 213 febrile episodes were randomly treated with either PIPC/TAZ 337.5 mg/kg/day, or CFPM 100 mg/kg/day. No significant differences were observed in the success rates of the PIPC/TAZ and CFPM treatments (62.1% vs. 59.1%, P = 0.650). Furthermore, no differences were noted in the rates of new infection and mortality, and no serious adverse effects occurred in either of groups. Both PIPC/TAZ and CFPM were effective and safe as an empirical therapy for FN in children. Pediatr Blood Cancer 2015;62:356–358. © 2014 Wiley Periodicals, Inc.
Impact of postoperative complications on overall survival of patients with hepatoblastoma
Authors: Becker Kristina , Furch Christiane , Schmid Irene , von Schweinitz Dietrich , Häberle Beate
Published: September 2014

Background

Complete resection of hepatoblastoma (HB) is a demanding procedure in advanced tumors. Perioperative complications are still common. The influence of complication rates on course of disease and survival of patients with HB has not been analyzed yet.

Procedures

Patients with high risk (HR) HB and standard‐risk (SR) HB registered from 1999 to 2008 to the German prospective multicenter study HB99 were evaluated regarding perioperative complications, reasons (e.g., tumor size and vessel involvement) and impact on further treatment and overall survival (OS).

Results

Surgical data from 126 patients were available (47 HR–HB, 79 SR–HB). Postoperative complications occurred in 26 (21%) patients consisting of biliary leakage (n = 9), cholestasis (n = 5), deficit of liver perfusion (n = 5) and others (n = 7). Twenty of these 26 patients (77%) required a second operation. The rate of postoperative complications was higher in the HR‐group (26%) compared to the SR‐group (17%). Patients with vessel involvement had significantly more complications (17% vs. 54%, P = 0.01). Patients with PRETEXT I/II‐tumors had the same rate of postoperative complications (19% vs. 20%) as patients with PRETEXT III/IV. Patients of HR‐group with postoperative complications showed delayed start in adjuvant chemotherapy (>21d) (75% vs. 25%, n.s.) combined with significant lower 5‐year‐OS (75% vs. 50%, P = 0.02). In multivariate analysis postoperative complications were an independent negative prognostic factor for HR‐patients (HR 3.1, P = 0.04).

Conclusions

Postoperative complications after HB resection are frequent and associated with worsened OS of patients with HR–HB. One possible reason is delay in postoperative chemotherapy. The approach to precarious liver resection should be carefully planned and executed by specialists. Pediatr Blood Cancer 2015;62:24–28. © 2014 Wiley Periodicals, Inc.
Synergistic Action of Alginate Chemical Reduction and Laser Irradiation for the Formation of Au Nanoparticles with Controlled Dimensions
Authors: Anyfantis George C. , Scotto Marco , Scarpellini Alice , Pignatelli Francesca , Toussi Setareh M. , Ruffilli Roberta , Martiradonna Luigi , Athanassiou Athanassia
Published: September 2014

Freestanding natural polymeric films with homogeneous dispersion of gold nanoparticles (Au NPs) are obtained via in situ reduction of gold(III) chloride trihydrate by sodium alginate (SA) biopolymer matrix, during water evaporation without the use of additional reducing agents. The size and size distribution of the prepared Au NPs can be tuned by changing the concentration of the precursor and/or the procedure of the films’ preparation. The nanocomposite films after preparation are stable in ambient conditions and can be used without the need of further processing, or can be redissolved in water. In the case of water dissolution, the aqueous solutions are irradiated with UV laser pulses turning the previously formed Au NPs into smaller ones with narrow size distributions through photofragmentation. This technique is proposed as a green way of synthesizing Au NPs of tunable size in aqueous solution of alginate, or incorporated in alginate freestanding polymeric films, that due to their biocompatibility can be used as passive labels or active sensors in biomedical applications.
Proteomics in paediatric cardiac surgery: Is a personalised approach feasible?
Authors: Hepponstall Michele , Konstantinov Igor E.
Published: September 2014

The incidence of congenital cardiac abnormalities remains high. Paediatric patients with congenital cardiac defects often require surgery at a young age. The surgeries are often long and complex, rendering this population particularly vulnerable to the deleterious effects of cardiopulmonary bypass and cardiac surgery. The search for cardioprotective strategies is ongoing in an attempt to reduce the morbidity in this population. In the post‐genomic era, it is apparent that simply determining the genomic sequences holds little diagnostic potential and means to determine progression of disease and response to treatment. The field of proteomics is expanding and application of proteomic techniques in the clinical setting holds great potential to advance our understanding of the proteomic changes involved in specific disease stages. This review will assess the application of proteomic techniques in the setting of paediatric cardiac surgery and highlight the need to obtain a clear understanding of the role of various proteins in children with cardiac conditions. The success and challenges of the available proteomic technology will be discussed as well as the future potential of proteomic methods for advancing our understanding of protein changes in children requiring cardiac surgery.