bluuebunny/crossref_metadata_2025 huggingface dataset:
Regioselective Cleavage of Thioether Linkages in Microcystin Conjugates
Authors: Zemskov Ivan , Kropp Heike M. , Wittmann Valentin
Published: June 2016

Microcystins are cyanobacterial toxins that can be found in fresh and coastal waters during algal blooms. Microcystin contamination of water can cause severe poisoning of animals and humans. Quantification of these toxins in biological samples is complicated because a major proportion of microcystins is covalently linked to proteins through thioether bonds formed through a Michael‐type addition of cysteine residues of proteins to an N‐methyldehydroalanine residue in the microcystins. We investigated chemical methods that can be used to cleave such thioether bonds by means of an elimination reaction that leaves the microcystin backbone intact for subsequent analysis. The known reagent O‐mesitylenesulfonylhydroxylamine (MSH) led to regioselective thioether cleavage, but a large excess of reagent was needed, thus making purification challenging. An unexpected side reaction observed during the investigation of the base‐induced elimination inspired us to develop a new thioether‐cleavage methodology based on the addition of propargylamine as a nucleophile that can trap the elimination product. This methodology could be successfully applied to the quantitative cleavage of a microcystin‐LF–glutathione conjugate. The alkyne moiety introduced by this procedure offers the possibility for further reactions with azides by using click chemistry, which might be useful for the derivatization or isolation of microcystins.
Two Different Pathways in the Reduction of [(S=)PCl(μ‐NtBu)]2 with Na
Authors: Bawari Deependra , Prashanth Billa , Ravi Satyam , Shamasundar K. R. , Singh Sanjay , Wright Dominic S.
Published: June 2016

Invited for the cover of this issue is the group of Sanjay Singh and Dominic S. Wright at the Indian Institute of Science Education and Research in Mohali and at the Cambridge University. The image depicts a sulfur‐bridged hexameric inorganic macrocycle along with stable 2D and 3D polymeric arrangements of a singlet biradicaloid dianion. Read the full text of the article at 10.1002/chem.201600839.
Correlation structure selection for longitudinal data with diverging cluster size
Authors: Wang Peng , Zhou Jianhui , Qu Annie
Published: June 2016

Correlation structure selection for non‐normal longitudinal data is very challenging for diverging cluster size because of the high‐dimensional correlation parameters involved and the complexity of the likelihood function for non‐normal longitudinal data. However identifying the correct correlation structure is important because it can improve estimation efficiency and testing power for longitudinal data. We propose to approximate the inverse of the empirical correlation matrix using a linear combination of candidate basis matrices, and select the correlation structure by identifying non‐zero coefficients of the basis matrices. This is carried out by minimizing penalized estimating functions, which balance the complexity and informativeness of modelling for the correlation matrix. The new approach does not require estimating each entry of the correlation matrix (except for an initial empirical estimate from the residuals), nor specifying the likelihood function, and can effectively handle non‐normal longitudinal data. The derivation of asymptotic theory for model selection consistency and oracle properties is challenging in the framework where the cluster size and the number of basis matrices are both diverging. Our numerical studies show that the proposed method performs satisfactorily for both normal and binary responses in this diverging framework.The Canadian Journal of Statistics44: 343–360; 2016 © 2016 Statistical Society of Canada
Fenton‐Like Degradation Comparison of s‐Triazine Herbicides in Aqueous Medium
Authors: Chen Tao , Liu Zhangyun , Yao Jinting , Hao Hongyuan , Chen Feng
Published: June 2016

Fenton‐like degradation of three representative s‐triazine herbicides, atrazine (Atz), ametryn (Amt), and prometon (Prt), was studied in this work. The effects of initial H2O2 concentration as well as the Fe3+ concentration on the degradation rate of the herbicides were investigated. The Fenton‐like degradation of the s‐triazine herbicides fitted well with pseudo first‐order kinetics. LCMS‐IT‐TOF was used to analyze possible degradation intermediates for the three herbicides. Eleven, eleven, and twelve intermediates were identified for Atz, Amt, and Prt, respectively. According to the identified intermediates, the Fenton‐like degradation pathways of Atz, Amt, and Prt were proposed, which were suggested to follow two main routes, alkylic oxidation and hydroxylation substitution. The enhanced electron‐donating ability of the s‐triazine herbicide benefits both degradation reaction routes. Therefore, Amt gives the highest reactivity, while Atz exhibits the highest resistance among three herbicides to the Fenton‐like reaction.
Human immunodeficiency virus‐associated lymphomas in the antiretroviral therapy era: Analysis of the National Cancer Data Base
Authors: Olszewski Adam J. , Fallah Jaleh , Castillo Jorge J.
Published: June 2016

BACKGROUND

Antiviral therapy has altered the prognosis of patients with human immunodeficiency virus (HIV)‐associated non‐Hodgkin lymphoma (NHL), but patterns of lymphoma‐directed therapy in the community are unknown.

METHODS

The authors analyzed the National Cancer Data Base records of 10,769 patients who were diagnosed with HIV‐associated lymphoma from 2004 through 2012. Changes in clinical characteristics and chemotherapy delivery over time were evaluated. Factors that were associated with not receiving chemotherapy were studied using multivariable logistic regression, reporting odds ratios (ORs) with 95% confidence intervals (CIs).

RESULTS

The proportion of black or Hispanic patients with HIV‐associated NHL increased from 41% in 2004 to 55% in 2012 (P < .0001). Chemotherapy was received by 81% of patients with diffuse large B‐cell lymphoma, 90% of those with Burkitt lymphoma, 61% of those with primary effusion lymphoma (PEL), and 35% of those with primary central nervous system lymphomas (PCNSL). Between 2004 and 2012, this proportion increased only for patients with PCNSL (P < .00001). Chemotherapy was less likely to be received by patients who were older, black, or without private insurance. It was delivered more frequently in hospitals designated as academic (OR for nonreceipt, 0.68; 95% CI, 0.51‐0.92) or in hospitals that had ≥3 HIV‐positive cases per year (OR, 0.71; 95% CI, 0.58‐0.86). Survival improved in patients with diffuse large B‐cell lymphoma (P = .007), Burkitt lymphoma (P = .0002), and PCNSL (P = .019), but not in those with PEL (P = .94). Receipt of chemotherapy in patients with PEL was not associated with better survival.

CONCLUSIONS

Disparities in chemotherapy delivery need attention, because a majority of HIV‐positive patients with NHL in the United States are now black or Hispanic. Higher volume centers were associated with an increased likelihood of chemotherapy administration. Survival gains in patients with PCNSL parallel an increase in chemotherapy use, supporting its role in therapy. [See Editorial on pages 000‐000, this issue.] Cancer 2016. © 2016 American Cancer Society. Cancer 2016;122:2689–2697. © 2016 American Cancer Society.
Coupling schemes for the FSI forward prediction challenge: Comparative study and validation
Authors: Landajuela Mikel , Vidrascu Marina , Chapelle Dominique , Fernández Miguel A.
Published: June 2016

This paper presents a numerical study in which several partitioned solution procedures for incompressible fluid‐structure interaction are compared and validated against the results of an experimental fluid‐structure interaction benchmark. The numerical methods discussed cover the three main families of coupling schemes: strongly coupled, semi‐implicit, and loosely coupled. Very good agreement is observed between the numerical and experimental results. The comparisons confirm that strong coupling can be efficiently avoided, via semi‐implicit and loosely coupled schemes, without compromising stability and accuracy. Copyright © 2016 John Wiley & Sons, Ltd.
On the Formation of N3H3 Isomers in Irradiated Ammonia Bearing Ices: Triazene (H2NNNH) or Triimide (HNHNNH)
Authors: Förstel Marko , Tsegaw Yetsedaw A. , Maksyutenko Pavlo , Mebel Alexander M. , Sander Wolfram , Kaiser Ralf I.
Published: June 2016

The remarkable versatility of triazenes in synthesis, polymer chemistry and pharmacology has led to numerous experimental and theoretical studies. Surprisingly, only very little is known about the most fundamental triazene: the parent molecule with the chemical formula N3H3. Here we observe molecular, isolated N3H3 in the gas phase after it sublimes from energetically processed ammonia and nitrogen films. Combining theoretical studies with our novel detection scheme of photoionization‐driven reflectron time‐of‐flight mass spectroscopy we can obtain information on the isomers of triazene formed in the films. Using isotopically labeled starting material, we can additionally gain insight in the formation pathways of the isomers of N3H3 under investigation and identify the isomers formed as triazene (H2NNNH) and possibly triimide (HNHNNH).
Combined Constant‐Force and Constant‐Velocity Single‐Molecule Force Spectroscopy of the Conrotatory Ring Opening Reaction of Benzocyclobutene
Authors: Kouznetsova Tatiana B. , Wang Junpeng , Craig Stephen L.
Published: June 2016

Single‐molecule force spectroscopy (SMFS) of multi‐mechanophore polymers has been used to provide kinetic and mechanistic insights into mechanochemical reactions. Whereas biological systems have benefitted from force clamp spectroscopy, synthetic polymers have been studied primarily with constant‐velocity methods. Here, force clamp SMFS is applied to the mechanically accelerated conrotatory ring opening of benzocyclobutene, and a comparison with constant‐velocity SMFS extends the range of available rate‐versus‐force data and corroborates the use of constant‐velocity SMFS to extract force dependencies.
Raman Spectroscopic Study on Alkyl Chain Conformation in 1‐Butyl‐3‐methylimidazolium Ionic Liquids and their Aqueous Mixtures
Authors: Singh Dheeraj K. , Cha Seoncheol , Nam Dahyun , Cheong Hyeonsik , Joo Sang‐Woo , Kim Doseok
Published: June 2016

Ionic liquids of 1‐butyl‐3‐methylimidazolium ([BMIM]) cation with different anions (Cl−, Br−, I−, and BF4−), and their aqueous mixtures were investigated by using Raman spectroscopy and dispersion‐included density functional theory (DFT). The characteristic Raman bands at 600 and 624 cm−1 for two isomers of the butyl chain in the imidazolium cation showed significant changes in intensity for different anions as well as in aqueous solutions. The area ratio of these two bands followed the order I−>Br−>Cl−>BF4− (in terms of the anion X in [BMIM]X), indicating that the butyl chain of [BMIM]I tends to adopt the trans conformation. The butyl chain was found to adopt the gauche conformation upon dilution, irrespective of the anion type. The Raman bands in the butyl C−H stretch region for [BMIM]X (X=Cl−, Br−, and I−) blueshifted significantly with the increase in the water concentration, whereas that for [BMIM]BF4 changed very little upon dilution. The blueshift in the C−H stretch region upon dilution also followed the order: [BMIM]I>[BMIM]Br>[BMIM]Cl>[BMIM]BF4, the same order as the above trans conformation preference of the butyl chain in pure imidazolium ionic liquids, which suggested that the cation‐anion interaction plays a role in determining the conformation of the chain.
On the Origin of Steep and Localized Radial Electric Field in the Transport Barrier at Plasma Edge
Authors: Itoh K. , Itoh S.‐I. , Kobayashi T. , Kamiya K. , Ido T. , Tokuzawa T. , Inagaki S. , Kasuya N.
Published: June 2016

Theories to understand the steep and localized radial electric field in the edge of toroidal plasma, which appears in conjunction with H‐mode, is revisited based on the electric field bifurcation model. Key elements in the models of the L‐H transition (including the toroidal effects on the dielectric constant and the effects of the curvature of radial electric field on turbulence suppression) are assessed. Results are applied to tokamak and helical plasmas, for which data with high‐resolution have been obtained recently. The status of quantitative tests on various mechanisms through comparison with experimental observations is also addressed. (© 2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Flow cytometry analysis of receptor internalization/shedding
Authors: Rigo Antonella , Vinante Fabrizio
Published: June 2016

Background

Differentiation, proliferation, and chemotaxis responses stem from biological programs that recognize checkpoints at the level of membrane receptor internalization and shedding. Therefore, receptor trafficking represents a crucial regulator of cell functions.

Methods

Here, we present a survey of analyses of receptor internalization vs. shedding based on simple flow cytometry‐based techniques. A relevant basic observation is that a fluorochrome‐bearing antibody bound to a specific receptor that is translocated from the membrane to the cytoplasm continues to emit light, i.e., the cell remains equally positive for that marker even if the receptor is strongly downregulated or no longer detectable on the membrane. In contrast, fluorescence is lost following receptor shedding.

Results

The combined uses of standardized hyperosmolar sucrose, acidic treatment and flow cytometry staining at different times allows for fully informative studies of the internalization or shedding pattern of a given receptor. The procedure can be simplified into a straightforward, simple‐to‐use, and flexible flow cytometry method based on two sequential steps with in‐between receptor stimulation. This method obviates the need for time‐consuming fluorescence techniques and even confocal microscopy.

Conclusion

We validate this procedure via comparisons of three receptors, i.e., CXCR4, CD30, and CD25, with membrane trafficking patterns that are involved in biological functions that are relevant to immunity and cancer. © 2016 International Clinical Cytometry Society
Use FlowRepository to share your clinical data upon study publication
Authors: Spidlen Josef , Brinkman Ryan R.
Published: June 2016

A fundamental tenet of scientific research is that published results including underlying data should be open to independent validation and refutation. Data sharing encourages collaboration, facilitates quality and reduces redundancy in data production. Authors submitting manuscripts to several journals have already adopted the habit of sharing their underlying flow cytometry data by deposition to FlowRepository—a data repository that is jointly supported by the International Society for Advancement of Cytometry, the International Clinical Cytometry Society and the European Society for Clinical Cell Analysis. De‐identification is required for publishing data from clinical studies and we discuss ways to satisfy data sharing requirements and patient privacy requirements simultaneously. Scientific communities in the fields of microarray, proteomics, and sequencing have been benefiting from reuse and re‐exploration of data in public repositories for over decade. We believe it is time that clinicians follow suit and that de‐identified clinical data also become routinely available along with published cytometry‐based findings. © 2016 International Clinical Cytometry Society
Interspecific interactions, population variation, and environmental forcing in the context of the community
Authors: Porzig Elizabeth L. , Seavy Nathaniel E. , Eadie John M. , Humple Diana L. , Geupel Geoffrey R. , Gardali Thomas
Published: June 2016

We evaluated the contribution of interspecific interactions, intraspecific processes, and environmental forcing to variation in speciessa' abundance in a habitat undergoing rapid successional change. We applied a Bayesian hierarchical approach to a 29‐yr time series of territory density of seven landbird species at a site in coastal California where secondary plant succession has occurred. We found that interspecific interactions were the least important driver in our system, explaining between 0% and 5% of variation. The combined effects of vegetation and rainfall variation explained 6% to 30% of variation in species trends. Intraspecific processes explained between 0% and 39% of variation. Between 27% and 90% of variation was attributed to unexplained variation. Our results demonstrate that in the system studied, interspecific interactions among landbirds are relatively unimportant. These results suggest that in some cases it may be valid to model projections of individual populations to predict community responses to future conditions; however, this conclusion should be interpreted with caution because interspecific interactions in our community did not include novel interactions that could result from distributional shifts in species ranges.
Distance decay of similarity in fungivorous insect communities: assessing dispersal limitation using genetic data
Authors: Kobayashi Takuya , Sota Teiji
Published: June 2016

We evaluated how dispersal limitation affected spatial variation in the species composition of fungivorous insect communities inhabiting fruiting bodies of bracket fungi on scattered deadwoods. The insect communities showed significant distance decay of similarity pattern among deadwoods, which was not fully explained by differences in environmental conditions. To investigate whether insect dispersal limitation could explain the distance‐decay pattern, we analyzed mitochondrial haplotype data; limited dispersal is expected to generate an isolation‐by‐distance pattern of genetic structure in component species. However, genetic distance between deadwoods was not correlated with geographic distance in any species, and a simulation study suggested that the absence of genetic structure refutes the dispersal limitation hypothesis even when the resolution of genetic differences is not high, as in our study. Thus, dispersal limitation did not contribute to the observed community patterns within our study site, suggesting that unmeasured environmental factors may have played an important role. Our study demonstrates that genetic data can help determine whether dispersal limitation of component species is the primary cause of observed distance decay in community similarity.
‘This way please’: Apoptotic cells regulate phagocyte migration before and after engulfment
Authors: Ariel Amiram , Ravichandran Kodi S.
Published: June 2016

Apoptotic leukocyte clearance is a hallmark of the resolution of inflammation and is a central fate‐determining event for macrophages. The directional migration of motile phagocytes toward cellular corpses and the subsequent engulfment are tightly regulated, and the exciting molecular mechanisms for these complex steps are actively under investigation. In this issue Angsana et al. [Eur. J. Immunol. 2016. 46: 1592‐1599.] report that the chemokine receptor CXCR4 is upregulated on murine and human macrophages following the engulfment of apoptotic cells, or following exposure to the pro‐resolving nucleotide adenosine. This work, together with other recent findings, point toward a new mode of regulation of macrophages following the engulfment of apoptotic cells. In this commentary, we put these findings in relevant perspective and highlight its potential ramifications.
A Promising Catalytic and Theranostic Agent Obtained through the In‐Situ Synthesis of Au Nanoparticles with a Reduced Polyoxometalate Incorporated within Mesoporous MIL‐101
Authors: Roch‐Marchal Catherine , Hidalgo Tania , Banh Hung , Fischer Roland A. , Horcajada Patricia
Published: June 2016

A well‐controlled three‐step green synthetic method allows the synthesis of composite materials based on the highly stable chromium(III) terephthalate MIL‐101(Cr) with gold nanoparticles (NPs) and polyoxometalates (POMs) inside its mesopores. First, the POM was included within the MIL‐101(Cr) cavities through the direct synthesis of MIL‐101(Cr) in the presence of the preformed H3PMo12O40 POM. Then, the incorporated POM was reduced in situ with H2. Finally, an in‐situ soft reduction of HAuCl4 by the reduced POM led to the formation of Au NPs and oxidized POM within the MIL‐101(Cr) structure [(Au)H2redPOM@101]. A final Au/POM atomic ratio of 1.8 was reached. The chemical and structural stabilities of both MIL‐101(Cr) and the POM were preserved during the whole process. In addition to the potential catalytic properties of these highly porous composite systems, we have demonstrated their promising performance as optical contrast agents. The (Au)H2redPOM@101 composites exhibited excellent biostability and were rapidly internalized in macrophage cells, as observed through fluorescence confocal microscopy.
Enzymatic Oxidative Tandem Decarboxylation of Dioic Acids to Terminal Dienes
Authors: Dennig Alexander , Kurakin Sara , Kuhn Miriam , Dordic Andela , Hall Mélanie , Faber Kurt
Published: June 2016

The biocatalytic oxidative tandem decarboxylation of C7–C18 dicarboxylic acids to terminal C5–C16 dienes was catalyzed by the P450 monooxygenase OleT with conversions up to 29 % for 1,11‐dodecadiene (0.49 g L–1). The sequential nature of the cascade was proven by the fact that decarboxylation of intermediate C6–C11 ω‐alkenoic acids and heptanedioic acid exclusively gave nonconjugated 1,4‐pentadiene; scale‐up allowed the isolation of 1,15‐hexadecadiene and 1,11‐dodecadiene; the system represents a short and green route to terminal dienes from renewable dicarboxylic acids.
Computational NMR as Useful Tool for Predicting Structure and Stereochemistry of Four‐Membered Sulfur Heterocycles
Authors: Pisano Luisa , Degennaro Leonardo , Carraro Massimo , Azzena Ugo , Fanelli Flavio , Mastrorilli Piero , Luisi Renzo
Published: June 2016

We report a computational NMR study of stereochemically challenging thietane 1‐oxides. Comparison of calculated and experimental data allows to assign structure and stereochemistry to the examined molecules. Computations included full conformational analysis of each thietane, DFT geometry optimizations and GIAO NMR calculations. Among the possible stereoisomers, only the computed structures with the correct stereochemistry were found to fit experimental NMR spectroscopic data. Computational analysis provide useful information on the conformational ring preference not easy to disclose by conventional structural analysis.
Cross Dehydrogenative Coupling (CDC) Reactions of N,N‐Disubstituted Formamides, Benzaldehydes and Cycloalkanes
Authors: Batra Aanchal , Singh Paramjit , Singh Kamal Nain
Published: June 2016

In recent years, reactions of inexpensive and easily available formamides, benzaldehydes and cycloalkanes with various coupling partners have made an impact in the field of cross dehydrogenative coupling. Even in the absence of a benzylic C–H site or a heteroatom at the α‐position, these substrates react efficiently under oxidative conditions. This review article highlights recent advances in cross dehydrogenative coupling reactions for C–C and C–heteroatom bond formation with the above substrates.
Synthetic Routes to TEG‐Substituted Diketopyrrolopyrrole‐Based Low Band‐Gap Polymers
Authors: Punzi Angela , Nicoletta Francesca , Marzano Giuseppe , Fortuna Cosimo G. , Dagar Janardan , Brown Thomas M. , Farinola Gianluca M.
Published: June 2016

We report herein general synthetic routes to novel TEG‐functionalized DPP‐based co‐polymers (TEG = triethylene glycol; DPP = diketopyrrolopyrrole) that display alternating TEG‐substituted DPP moieties with various functionalized donor units; donor units contain moieties such as polythiophene segments decorated with thermocleavable tertiary esters or additional TEG chains and alkoxy‐substituted benzodithiophenes. The synthetic approaches are based on Stille coupling chemistry or, for the first time for TEG‐substituted DPP‐based polymers, on direct heteroarylation polymerizations. Spectroscopic and electrochemical characterization as well as preliminary tests in photovoltaic cells are also reported.
Diversity‐Oriented Synthesis and Biological Evaluation of Iminosugars from Unprotected 2‐Deoxy‐d‐ribose
Authors: Malinowski Maciej , Rowicki Tomasz , Guzik Patrycja , Wielechowska Monika , Sobiepanek Anna , Sas Wojciech
Published: June 2016

An exceptionally short synthesis of novel indolizidine‐, quinolizidine‐, and piperidine‐based iminosugars from unprotected 2‐deoxy‐d‐ribose by intramolecular 1,3‐dipolar cycloaddition of sugar‐derived N‐(3‐alkenyl)nitrones has been accomplished. The use of the 2‐deoxy carbohydrate also enabled us to confirm the previously proposed mechanism for the alteration of the stereochemical course of the intramolecular 1,3‐dipolar cycloaddition observed for an unprotected sugar‐derived nitrone. Biological assays of the six new iminosugars revealed a slight inhibition activity of the indolizidine derivative 7a, whereas, interestingly, the two quinolizidine iminosugars 5a and 5b appeared to be weak glycosidase activators.
Strigolactone Analogues with a D‐Ring Modified at C‐2
Authors: Mwakaboko Alinanuswe S. , Zwanenburg Binne
Published: June 2016

Strigolactones (SLs) are important new plant hormones that receive much attention in current plant science. SLs are produced by many plants and are exuded by the root system. SLs are, amongst others, germination stimulants for seed of parasitic weeds. Naturally occurring SLs invariably contain three annelated rings, the ABC‐scaffold, connected to a butenolide (the D‐ring) via an enol ether unit. The synthesis of natural SLs requires many steps, therefore there is a continuous search for SL analogues with a simpler structure but with retention of bioactivity. In this study modified D‐ring variants are investigated, especially analogues having a methyl group at C‐2 instead of a hydrogen. For these analogues the ABC‐scaffolds of GR24 and Nijmegen‐1 were used. The coupling reaction proceeds profoundly better with chlorobutenolides than with the corresponding bromides. Bioassays reveal that the introduction an extra methyl at C‐2 does not influence the germination activity, which is relevant for gaining insight in the mode of action of SLs.
Pd‐Catalyzed Directed Chlorination of Unactivated C(sp3)–H Bonds at Room Temperature
Authors: Xiong Heng‐Ying , Cahard Dominique , Pannecoucke Xavier , Besset Tatiana
Published: June 2016

A Pd‐catalyzed directed chlorination of unactivated C(sp3)–H bonds has been developed. By using the bidentate 8‐aminoquinolinyl directing group, selective chlorination of aliphatic amides has been achieved in moderate to good yields at room temperature in the presence of N‐chlorosuccinimide (NCS). This approach offers access to valuable chlorinated molecules, key building blocks for bulk and fine chemical industry. Moreover, the dichlorination reaction has also been studied. The synthetic utility of the chlorinated products was further demonstrated through their conversion into β‐lactams.
Electrochemical Capacitive K+ EMIS Chemical Sensor Based on the Dibromoaza[7]helicene as an Ionophore for Potassium Ions Detection
Authors: Tounsi Moncef , Ben Braiek Mourad , Baraket Abdoullatif , Lee Michael , Zine Nadia , Zabala Miguel , Bausells Joan , Aloui Faouzi , Ben Hassine Béchir , Maaref Abderrazak , Errachid Abdelhamid
Published: June 2016

A K+‐sensitive capacitive electrolyte‐membrane‐insulator‐semiconductor (EMIS) based on a novel dibromoaza[7]helicene ionophore has been developed. An ion‐sensitive membrane based on polyvinylchloride (PVC) doped with the ionophore was deposited on the Si3N4/SiO2/Si‐p/Cu‐Al transducer. The properties of the K+‐EMIS chemical sensor were investigated by electrochemical impedance spectroscopy (EIS). All the developed devices upon being tested have shown good sensitivity and linearity responses within the range 10−6 M to 10−1 M of potassium activity, with good selectivity over a wide variety of other cations (Na+, Li+, Cu2+, Ca2+, and Mg2+). To our knowledge, this is the first time that a capacitive field‐effect sensor has been fabricated using helicene as a carrier for K+‐detection, combined with the structure: Si3N4/SiO2/Si‐p/Cu‐Al as a transducer.
Application of Localized Electrochemical Impedance Spectroscopy to Lithium‐Ion Cathodes and in situ Monitoring of the Charging Process
Authors: Harms Nina , Heins Tom P. , Schröder Uwe
Published: June 2016

Localized electrochemical techniques, which have been developed for the last few decades, are useful tools for the examination of surface properties and processes in many different fields of research. Especially localized electrochemical impedance spectroscopy (LEIS) is a promising technique for many applications, as it combines the advantages of conventional electrochemical impedance spectroscopy (EIS) and localized techniques. In this study, requirements and difficulties regarding the application of LEIS to lithium ion electrodes are illustrated and different aspects of a useful experimental setup are introduced. Furthermore, some basic observations regarding the development of the system's Ohmic and charge transfer resistances during the electrode's charging process are presented.
Granular activated carbon as a particle electrode in three‐dimensional electrochemical treatment of reactive black B from aqueous solution
Authors: Sowmiya Sakthivel , Gandhimathi Rajan , Ramesh Sreekrishnaperumal Thanga , Nidheesh Puthiya Veetil
Published: June 2016

The present study focuses on the efficiency of three‐dimensional (3D) electrochemical treatment of Reactive Black B (RBB) from aqueous solution. Graphite plate was used as both anode and cathode. Granular activated carbon (GAC) was used as the particle electrode. The decolorization efficiency increased with the increase in NaCl dosage and cell voltage. The reactions were favored by the acidic pH. Complete removal of RBB (having initial dye concentration of 100 mg/L) was observed for 5 g of GAC and 58.5 mg/L of electrolyte at pH 3 and cell voltage of 10 V. For this test, 74% of mineralization was observed and the decolorization followed the pseudo‐first‐order kinetics. The 3D electrochemical treatment was proved to be efficient in the RBB dye degradation. © 2016 American Institute of Chemical Engineers Environ Prog, 35: 1616–1622, 2016
Two New Ring A‐Cleaved Lanostane‐Type Triterpenoids and Four Known Steroids Isolated from Endophytic Fungus Glomerella sp. F00244
Authors: Guo Kai , Fang Huiqin , Gui Fu , Wang Yuezhou , Xu Qinyan , Deng Xianming
Published: June 2016

Two new ring A‐cleaved lanostane‐type triterpenoids, glometenoid A (1) and glometenoid B (2), together with four known steroids, (20S,22E,24R)‐ergosta‐7,22‐dien‐3β,5α,6β‐triol (3), (3β,5α,8α,22E)‐ergosta‐6,22‐diene‐3,5,8‐triol (4), 5α,8α‐epidioxy‐22E‐ergosta‐6,22‐dien‐3β‐ol (5), and ergosterol (6), were isolated from the endophytic fungus Glomerella sp. F00244. Their structures were elucidated by comprehensive spectroscopic analyses of NMR and MS data. Their antimicrobial activities were evaluated against pathogenic bacteria Bacillus subtilis ATCC 9372, Staphylococcus aureus ATCC 25923, Bacillus pumilus CMCC (B) 63202, Micrococcus luteus CMCC28001, and pathogenic fungi Candida albicans AS2.538 and Aspergillus niger ACCC30005, but no inhibition was observed at a concentration of 20 μg/ml. Further cytotoxicity assessment revealed that compound 1 exhibited weak antiproliferative activity against ovarian cancer HeLa cell.
Mortality and Causes of Death in Patients With Osteogenesis Imperfecta: A Register-Based Nationwide Cohort Study
Authors: Folkestad Lars , Hald Jannie Dahl , Canudas-Romo Vladimir , Gram Jeppe , Hermann Anne Pernille , Langdahl Bente , Abrahamsen Bo , Brixen Kim
Published: June 2016

Osteogenesis imperfecta (OI) is a hereditary connective tissue disease that causes frequent fractures. Little is known about causes of death and length of survival in OI. The objective of this work was to calculate the risk and cause of death, and the median survival time in patients with OI. This study was a Danish nationwide, population-based and register-based cohort study. We used National Patient Register data from 1977 until 2013 with complete long-term follow-up. Participants comprised all patients registered with the diagnosis of OI from 1977 until 2013, and a reference population matched five to one to the OI cohort. We calculated hazard ratios for all-cause mortality and subhazard ratios for cause-specific mortality in a comparison of the OI cohort and the reference population. We also calculated all-cause mortality hazard ratios for males, females, and age groups (0 to 17.99 years, 18.00 to 34.99 years, 35.00 to 54.99 years, 55.00 to 74.99 years, and >75 years). We identified 687 cases of OI (379 women) and included 3435 reference persons (1895 women). A total of 112 patients with OI and 257 persons in the reference population died during the observation period. The all-cause mortality hazard ratio between the OI cohort and the reference population was 2.90. The median survival time for males with OI was 72.4 years, compared to 81.9 in the reference population. The median survival time for females with OI was 77.4 years, compared to 84.5 years in the reference population. Patients with OI had a higher risk of death from respiratory diseases, gastrointestinal diseases, and trauma. We were limited by the lack of clinical information about phenotype and genotype of the included patients. Patients with OI had a higher mortality rate throughout their life compared to the general population. © 2016 American Society for Bone and Mineral Research.
Development and Validation of Voriconazole Concentration by LC‐MS‐MS: Applied in Clinical Implementation
Authors: Prommas Santirat , Puangpetch Apichaya , Jenjirattithigarn Nuttawut , Chuwongwattana Sumonrat , Jantararoungtong Thawinee , Koomdee Napatrupron , Santon Siwalee , Chamnanphon Montri , Sukasem Chonlaphat
Published: June 2016

Background

Voriconazole (VRZ) is a triazole antifungal used for treatment of invasive fungal infection, which is a life‐threatening condition. Therapeutic drug monitoring is recommended for identifying the optimal dose in patients who have hepatic/renal impairment or reduced function of the CYP2C19 metabolizing enzyme.

Methods

One hundred microliters of sample plasma was extracted by protein precipitated with 200 μl of acetonitrile containing fluconazole as internal standard (IS). After vortexing and centrifugation, supernatant was dried and reconstituted with 100 μl of mobile phase (ACN: 0.1% formic acid in 10 mM Ammonium acetate) (50:50 v/v) before injected. The column was C18, 2.7 μm, 3.0 × 50 mm at flow rate of 0.5 ml/min with retention time of 0.5 and 0.75 min for VRZ and IS, respectively. The tandem mass spectrometer was set in multiple reactions monitoring (MRM) mode with the following transition; VRZ m/z 350.10→281.10 and 307.20→220.20 (IS).

Results

The accuracy and precision inter‐ and intra‐day were less than 9%, over the range 0.05–10 μg/ml. The linearity was consistent (r2 = 0.9987) and recovery was more than 85.0% for both analyses.

Conclusion

This method is applicable for routine monitoring of patients’ VRZ plasma level with fast and accurate runtime to assess CYP2C19 genotype.
ICOADS Release 3.0: a major update to the historical marine climate record
Authors: Freeman Eric , Woodruff Scott D. , Worley Steven J. , Lubker Sandra J. , Kent Elizabeth C. , Angel William E. , Berry David I. , Brohan Philip , Eastman Ryan , Gates Lydia , Gloeden Wolfgang , Ji Zaihua , Lawrimore Jay , Rayner Nick A. , Rosenhagen Gudrun , Smith Shawn R.
Published: June 2016

We highlight improvements to the International Comprehensive Ocean‐Atmosphere Data Set (ICOADS) in the latest Release 3.0 (R3.0; covering 1662–2014). ICOADS is the most widely used freely available collection of surface marine observations, providing data for the construction of gridded analyses of sea surface temperature, estimates of air–sea interaction and other meteorological variables. ICOADS observations are assimilated into all major atmospheric, oceanic and coupled reanalyses, further widening its impact. R3.0 therefore includes changes designed to enable effective exchange of information describing data quality between ICOADS, reanalysis centres, data set developers, scientists and the public. These user‐driven innovations include the assignment of a unique identifier (UID) to each marine report – to enable tracing of observations, linking with reports and improved data sharing. Other revisions and extensions of the ICOADS' International Maritime Meteorological Archive common data format incorporate new near‐surface oceanographic data elements and cloud parameters. Many new input data sources have been assembled, and updates and improvements to existing data sources, or removal of erroneous data, made. Coupled with enhanced ‘preliminary’ monthly data and product extensions past 2014, R3.0 provides improved support of climate assessment and monitoring, reanalyses and near‐real‐time applications.
Complete metastasectomy for renal cell carcinoma: Comparison of five solid organ sites
Authors: Jakubowski Christopher D. , Vertosick Emily A. , Untch Brian R. , Sjoberg Daniel , Wei Elizabeth , Palmer Frank L. , Patel Snehal G. , Downey Robert J. , Strong Vivian E. , Russo Paul
Published: June 2016

Background and Objectives

Patients with metastatic RCC can undergo metastasectomy to improve survival time. Our goal was to provide and compare characteristics and oncological outcomes of RCC patients who underwent complete metastasectomy at a single organ site.

Methods

A total of 138 RCC patients were identified as undergoing complete metastasectomy at a single organ site including adrenal, lung, liver, pancreas, or thyroid. Competing risk regression analysis was used to assess RFS and CSS adjusting for several covariates.

Results

In this highly selected cohort, RFS and CSS was 27% and 84% at 5 years following metastasectomy, respectively. Univariate analysis revealed that removal of multiple tumors, younger age, and a shorter interval between nephrectomy and metastasis was associated with worse RFS. Larger tumors and sarcomatoid histology at nephrectomy was associated with worse CSS. We found no evidence that metastases at the time of RCC diagnosis influenced recurrence or survival. Tumor size, number of metastases resected, and time from nephrectomy to first recurrence was significantly different, but recurrence rates were not found to be significantly different, when compared across all organ sites.

Conclusions

These findings inform clinical and surgical management of select RCC patients with isolated metastasis to one of several organ sites. J. Surg. Oncol. 2016;114:375–379. © 2016 Wiley Periodicals, Inc.
Active middle ear implant coupled bilaterally to the round window despite bilateral implanted stapes prostheses
Authors: Coordes Annekatrin , Jahreiss Linda , Schönfeld Uwe , Lenarz Minoo
Published: June 2016

After stapes surgery, patients with mixed or moderate hearing loss have limited possibilities for hearing improvement. We are reporting on a patient who underwent stapedotomy bilaterally 20 years ago and had sensorineural and mixed hearing loss. Recurrent otitis externa prevented the use of hearing aids. This patient was treated bilaterally with the Vibrant Soundbridge (Med‐El, Innsbruck, Austria) successively. The Schuknecht piston stapes prostheses remained in situ. The Floating Mass Transducer (FMT; Med‐El) was coupled to the round window (RW) and provided good acoustic reinforcement bilaterally. In conclusion, for patients with otosclerosis and stapes surgery, the FMT–RW coupling (Bess AG, Berlin, DE) is a safe procedure with good acoustic amplification. Laryngoscope, 2016 127:500–503, 2017
Midline posterior glossectomy and lingual tonsillectomy in obese and nonobese children with down syndrome: Biomarkers for success
Authors: Propst Evan J. , Amin Reshma , Talwar Natasha , Zaman Michele , Zweerink Allison , Blaser Susan , Zaarour Christian , Luginbuehl Igor , Karsli Cengiz , Aziza Albert , Forrest Christopher , Drake James , Narang Indra
Published: June 2016

Objectives/Hypothesis

To examine outcomes following midline posterior glossectomy (MPG) plus lingual tonsillectomy (LT) for the treatment of significant obstructive sleep apnea (OSA) in children with Down syndrome (DS).

Methods

Patients with DS who had persistent OSA following tonsillectomy and adenoidectomy (TA) and were relatively intolerant of positive airway pressure (PAP) therapy were evaluated by physical examination and sleep/CINE magnetic resonance imaging to determine the etiology of upper airway obstruction. Patients with relative macroglossia underwent MPG plus LT if required. Successful surgical outcome was defined as the resolution of OSA or the ability to tolerate PAP.

Results

Thirteen children (8 male, 5 female), mean (standard deviation) age 14.2 (4.0) years underwent MPG plus LT. Fifty‐four percent of patients were obese (Body mass index [BMI] > 95th centile) and 8% were overweight (BMI 85th–95th centile) preoperatively. All patients underwent pre‐ and postoperative polysomnography. Postoperatively, the obstructive apnea‐hypopnea index fell significantly from 47.0/hour to 5.6/hour (P <.05) in normal weight individuals who did not become obese, but not in obese patients or those who became obese postoperatively. Successful surgical outcome was seen in all (N = 6) children who were normal weight or overweight preoperatively compared with none who were obese preoperatively (N = 7).

Conclusion

Midline posterior glossectomy and LT are beneficial in normal weight and overweight children with DS who have persistent OSA following TA and are intolerant of PAP therapy. Obesity pre‐ or postoperatively portends a worse prognosis following MPG, suggesting that aggressive weight loss initiatives should be considered as an adjunct to surgery in this population.

Level of Evidence

4. Laryngoscope, 127:757–763, 2017
Bio‐Inspired Coating Strategies for the Immobilization of Polymyxins to Generate Contact‐Killing Surfaces
Authors: Alves Diana , Pereira Maria Olívia
Published: June 2016

Microbial colonization of indwelling devices remains a major concern in modern healthcare. Developing approaches to prevent biomaterial‐associated infections (BAI) is, therefore, in great demand. This study aimed to immobilize two antimicrobial peptides (polymyxins B and E) onto polydimethylsiloxane (PDMS) using two polydopamine (pDA)‐based approaches: the conventional two‐step method involving the deposition of a pDA layer to which biomolecules are immobilized, and a one‐step method where peptides are dissolved together with dopamine before its polymerization. Surface characterization confirms the immobilization of polymyxins onto PDMS at a non‐toxic concentration. Immobilization of polymyxins using a one‐step pDA‐based approach is able to prevent Pseudomonas aeruginosa adhesion and kill a significant fraction of the adherent ones. Living cells adhered to these modified surfaces exhibit the same susceptibility pattern as cells adhered to unmodified surfaces, highlighting no resistance development. Results suggest that polymyxins immobilization holds a great potential as an additional antimicrobial functionality in the design of biomaterials.

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A note on Riemann problems for single‐periodic polyanalytic functions
Authors: Han Pengju , Wang Yufeng
Published: June 2016

In this article, a new canonical function has been established to deal with Riemann boundary‐value problem of periodic analytic functions discussed in . In comparison with the corresponding result in , the expression of solution obtained here is much simpler. Then, we demonstrate the equivalence of solutions for the homogeneous Riemann problem. What's more, we obtain the precise rank of matrix of coefficients for the system of linear algebraic equations (4.35) in . Those results can simplify the discussion of Riemann problem of single‐periodic polyanalytic functions in .
Diet, gut microbes, and the pathogenesis of inflammatory bowel diseases
Authors: Dolan Kyle T. , Chang Eugene B.
Published: June 2016

The rising incidence of inflammatory bowel diseases in recent decades has notably paralleled changing lifestyle habits in Western nations, which are now making their way into more traditional societies. Diet plays a key role in IBD pathogenesis, and there is a growing appreciation that the interaction between diet and microbes in a susceptible person contributes significantly to the onset of disease. In this review, we examine what is known about dietary and microbial factors that promote IBD. We summarize recent findings regarding the effects of diet in IBD epidemiology from prospective population cohort studies, as well as new insights into IBD‐associated dysbiosis. Microbial metabolism of dietary components can influence the epithelial barrier and the mucosal immune system, and understanding how these interactions generate or suppress inflammation will be a significant focus of IBD research. Our knowledge of dietary and microbial risk factors for IBD provides important considerations for developing therapeutic approaches through dietary modification or re‐shaping the microbiota. We conclude by calling for increased sophistication in designing studies on the role of diet and microbes in IBD pathogenesis and disease resolution in order to accelerate progress in response to the growing challenge posed by these complex disorders.
Early detection of breast tumors using UWB microstrip antenna imaging
Authors: Karli Radouane , Ammor Hassan , Virdee Bal S.
Published: June 2016

This paper describes the detection of tumors in human breast tissues using an UWB planar antenna operating at a frequency recommended by FCC. The antenna has a measured bandwidth from 3.92 GHz to 11.32 GHz for |S11| < 10 dB. The detection technique is based on using the fact that the tumor's electrical properties, in particular conduction and specific absorption rate (SAR), change significantly from those of healthy biological tissue when exposed to microwave radiation. The hemispherical breast model used comprised breast skin, fat and the tumor tissue. Investigation was done with the tumor located at several positions inside the heterogeneous breast model. The patch antenna was operated in its near field by placed it in contact with the breast to enhance its sensitivity. High current density has been observed for various positions and sizes of the deep seated tumor while keeping SAR within safe limits specified by FCC of 1.6 W/Kg. A comparison technique is used to identify whether or not tumor (benign or malignant) is present in the breast. The results reveal the validity of the proposed simple and effective technique. © 2016 Wiley Periodicals, Inc. Microwave Opt Technol Lett 58:2101–2106, 2016
A high‐efficiency 60‐GHz indirect local oscillator in 90‐nm CMOS
Authors: Byeon Chul Woo , Park Chul Soon
Published: June 2016

This letter presents a highly efficient 60‐GHz local oscillator (LO) in a 90‐nm CMOS. The proposed LO consists a 30‐GHz LC VCO and a frequency doubler. With this topology, the LO generator has a high output power of −0.1 dBm at 58.2 GHz, consuming only 10.4 mW from a 0.8 V supply, resulting in a record efficiency of 9.4% among 60‐GHz CMOS LOs. At 58.2 GHz, the phase noise is −115 dBc/Hz at a 10‐MHz offset. The measured frequency tuning range is from 57.56 to 64.47 GHz. © 2016 Wiley Periodicals, Inc. Microwave Opt Technol Lett 58:2091–2093, 2016