bluuebunny/crossref_metadata_2025 huggingface dataset:
Abdominal Trigger Points and Psychological Function
Authors: Reeves Roy R. , Ladner Mark E.
Published: February 2016

Myofascial trigger points (TPs) are a poorly understood phenomenon involving the myofascial system and its related neural, lymphatic, and circulatory elements. Compression or massage of a TP causes localized pain and may cause referred pain and autonomic phenomena. The authors describe a 58-year-old woman who experienced precipitation of substantial psychological symptoms directly related to her treatment for a lower abdominal TP. Her symptoms resolved after 2 weeks of receiving high-velocity, low-amplitude manipulation and soft tissue massage. Particularly in the abdomen, TPs may be associated with psychological reactions as well as physical aspects of bodily function.
Poultry consumption and prostate cancer risk: a meta-analysis
Authors: He Qian , Wan Zheng-ce , Xu Xiao-bing , Wu Jing , Xiong Guang-lian
Published: February 2016

Background.Several kinds of foods are hypothesized to be potential factors contributing to the variation of prostate cancer (PCa) incidence. But the effect of poultry on PCa is still inconsistent and no quantitative assessment has been published up to date. So we conducted this meta-analysis to clarify the association between them.

Materials and Methods. We conducted a literature search of PubMed and Embase for studies examining the association between poultry consumption and PCa up to June, 2015. Pooled risk ratio (RR) and corresponding 95% confidence interval (CI) of the highest versus lowest poultry consumption categories were calculated by fixed-effect model or random-effect model.

Results.A total of 27 (12 cohort and 15 case-control) studies comprising 23,703 cases and 469,986 noncases were eligible for inclusion. The summary RR of total PCa incidence was 1.03 (95% CI [0.95–1.11]) for the highest versus lowest categories of poultry intake. The heterogeneity between studies was not statistically significant (P= 0.768,I2= 28.5%). Synthesized analysis of 11 studies on high stage PCa and 8 studies on chicken exposure also demonstrated null association. We also did not obtain significant association in the subgroup of cohort study (RR = 1.04, 95% CI [0.98–1.10]), as well as in the subgroups of population-based case-control study and hospital-based case-control study. Then the studies were divided into three geographic groups: Western countries, Asia and South America. The pooled RRs in these areas did not reveal statistically significant association between poultry and PCa.

Conclusions.This meta-analysis suggests no association between poultry consumption and PCa risk. Further well-designed studies are warranted to confirm the result.
Analysis of Protein Sumoylation
Authors: Sarge Kevin D.
Published: February 2016

Sumoylation, wherein small ubiquitin‐like modifier (SUMO) proteins are covalently attached to specific lysine residues of target proteins, plays an important role in regulating many diverse cellular processes via its control of the functional properties of the modified proteins. Identification of new sumoylated proteins is expected to expand understanding of the role this modification has in cell function. This unit describes two different assays for determining whether a particular protein is sumoylated: the first method employs immunoprecipitation of the protein followed by SUMO immunoblot. The second involves incubating the protein (either an in vitro translation product or a purified recombinant protein) with a reconstituted in vitro sumoylation reaction followed by examination for increased molecular‐weight bands in SDS‐PAGE as sumoylated forms of the protein. Either of these approaches can also be used to determine the sumoylated lysine residue(s) by comparing modification of the normal protein versus lysine‐to‐arginine substitutions of potential sumoylation sites, which once determined allows analysis of the effect of sumoylation on the protein's function. © 2016 by John Wiley & Sons, Inc.
Charisma counts: the presence of great apes affects the allocation of research effort in the paleotropics
Authors: Marshall Andrew J , Meijaard Erik , Van Cleave Eric , Sheil Douglas
Published: February 2016

Scientific research in the biodiversity‐rich paleotropics (the tropical portions of the Old World) provides multiple benefits, yet we know little about the distribution of research effort in this region and the factors that determine it. We used Google Scholar to assess paleotropical research effort – defined here as the number of published studies that reference one of 565 terrestrial protected areas in the 23 African and Asian countries that contain great apes (Gorilla spp, Pan spp, and Pongo spp). We found that research effort is strongly skewed toward a small number of sites and that most protected areas are inadequately represented in the scientific literature. Scientists conducting paleotropical research often focus their efforts on protected areas that are large, that are designated as national parks, and that contain non‐human great apes. Our results highlight important gaps in research effort, and indicate that current understanding of tropical protected areas is limited and heavily biased toward specific sites, many of which may not be representative of existing protected areas in the paleotropics.
Aminoacyl‐tRNA synthetases and the evolution of coded peptide synthesis: the Thioester World
Authors: Jakubowski Hieronim
Published: February 2016

Coded peptide synthesis must have been preceded by a prebiotic stage, in which thioesters played key roles. Fossils of the Thioester World are found in extant aminoacyl‐tRNA synthetases (AARSs). Indeed, studies of the editing function reveal that AARSs have a thiol‐binding site in their catalytic modules. The thiol‐binding site confers the ability to catalyze aminoacyl~coenzyme A thioester synthesis and peptide bond formation. Genomic comparisons show that AARSs are structurally related to proteins involved in sulfur and coenzyme A metabolisms and peptide bond synthesis. These findings point to the origin of the amino acid activation and peptide bond synthesis functions in the Thioester World and suggest that the present‐day AARSs had originated from ancestral forms that were involved in noncoded thioester‐dependent peptide synthesis.
Permafrost thaw and wildfire: Equally important drivers of boreal tree cover changes in the Taiga Plains, Canada
Authors: Helbig M. , Pappas C. , Sonnentag O.
Published: February 2016

Boreal forests cover vast areas of the permafrost zones of North America, and changes in their composition and structure can lead to pronounced impacts on the regional and global climate. We partition the variation in regional boreal tree cover changes between 2000 and 2014 across the Taiga Plains, Canada, into its main causes: permafrost thaw, wildfire disturbance, and postfire regrowth. Moderate Resolution Imaging Spectroradiometer Percent Tree Cover (PTC) data are used in combination with maps of historic fires, and permafrost and drainage characteristics. We find that permafrost thaw is equally important as fire history to explain PTC changes. At the southern margin of the permafrost zone, PTC loss due to permafrost thaw outweighs PTC gain from postfire regrowth. These findings emphasize the importance of permafrost thaw in controlling regional boreal forest changes over the last decade, which may become more pronounced with rising air temperatures and accelerated permafrost thaw.
A new model of amplitude fluctuations for radio propagation in solar corona during superior solar conjunction
Authors: Xu Guanjun , Song Zhaohui
Published: February 2016

Radio communication links through the solar corona are disturbed by electron density fluctuations caused by coronal turbulence. This has become a problem for deep space exploration when the spacecraft is near superior conjunction with the Sun. With a forecast of the signal fluctuations the link could be adapted to compensate for these impairments in real time. Motivated by this need, we present a theoretical study of the signal fluctuations including an analytical expression for the amplitude fluctuations. The proposed model includes an anisotropic spectrum of density fluctuations, the solar wind “outer scale,” and the spectral exponent. The performance of this analytical solution is demonstrated by comparison with published data from spacecraft and with other existing analytical methods.
Free‐Standing Functionalized Graphene Oxide Solid Electrolytes in Electrochemical Gas Sensors
Authors: Jiang Gaopeng , Goledzinowski Maciej , Comeau Felix J. E. , Zarrin Hadis , Lui Gregory , Lenos Jared , Veileux Alicia , Liu Guihua , Zhang Jing , Hemmati Sahar , Qiao Jinli , Chen Zhongwei
Published: February 2016

A free‐standing sulfonic acid functionalized graphene oxide (fSGO)‐based electrolyte film is prepared and used in an electrochemical gas sensor, an alcohol fuel cell sensor (AFCS), for the detection of alcohol. The fSGO electrolyte film‐based AFCS detects ethanol vapor with excellent response, linearity, and sensitivity, since it possesses a high proton conductivity (58 mS cm−1 at 55 °C). An ethanol detection limit level as low as 25 ppm is achieved and high selectivity for ethanol over acetone is demonstrated. These results do not only show the promising potential of fSGO films in an electrochemical gas sensors, specifically a portable breathalyzer, but also open an alternative pathway to investigate the application of graphene derivatives in the field of gas sensors.
Design of Novel Visible Light Active Photocatalyst Materials: Surface Modified TiO2
Authors: Nolan Michael , Iwaszuk Anna , Lucid Aoife K. , Carey John J. , Fronzi Marco
Published: February 2016

Work on the design of new TiO2based photocatalysts is described. The key concept is the formation of composite structures through the modification of anatase and rutile TiO2with molecular‐sized nanoclusters of metal oxides. Density functional theory (DFT) level simulations are compared with experimental work synthesizing and characterizing surface modified TiO2. DFT calculations are used to show that nanoclusters of metal oxides such as TiO2, SnO/SnO2, PbO/PbO2, ZnO and CuO are stable when adsorbed at rutile and anatase surfaces, and can lead to a significant red shift in the absorption edge which will induce visible light absorption; this is the first requirement for a useful photocatalyst. The origin of the red shift and the fate of excited electrons and holes are determined. For p‐block metal oxides the oxidation state of Sn and Pb can be used to modify the magnitude of the red shift and its mechanism. Comparisons of recent experimental studies of surface modified TiO2that validate our DFT simulations are described. These nanocluster‐modified TiO2structures form the basis of a new class of photocatalysts which will be useful in oxidation reactions and with a correct choice of nanocluster modified can be applied to other reactions.
Novel 14q11.2 microduplication including the CHD8 and SUPT16H genes associated with developmental delay
Authors: Smyk Marta , Poluha Anna , Jaszczuk Ilona , Bartnik Magdalena , Bernaciak Joanna , Nowakowska Beata
Published: February 2016

Neurodevelopmental disorders have long been associated with chromosomal abnormalities, including microdeletions and microduplications. Submicroscopic 14q11.2 deletions involving the CHD8 and SUPT16H genes have been reported in patients with developmental delay (DD)/intellectual disability (ID) or autism spectrum disorders (ASDs) and/or macrocephaly. Recently, disruptive CHD8 mutations were described in patients with similar phenotypes further showing pivotal role of CHD8 gene in the pathogenesis of DD/ID or ASDs. We report here the first case of ∼445 kb de novo microduplication, encompassing the minimal critical 14q11.2 deletion region, in 8‐year‐old boy showing DD, cognitive impairment and facial dysmorphism. Our results suggest that gain of the chromosomal region 14q11.2 is causative for clinical findings present in the patient. © 2016 Wiley Periodicals, Inc.
Unusual Products from Oxidation of Naphthalene Diimides
Authors: Maniam Subashani , Sandanayake Saman , Izgorodina Ekaterina I. , Langford Steven J.
Published: February 2016

Transforming the naphthalene diimide (NDI) core into unusual aromatic systems has large potential for applications in which current NDI‐based systems show promise. Treatment of N,N‐dialkylNDIs under mild oxidizing conditions with ruthenium(III) chloride and sodium periodate affords the corresponding 1,4‐diones in good yield. Interestingly, while aliphatic substituents at the N‐imide positions allowed oxidation to take place easily, the presence of neutral, electron‐rich or electron‐deficient phenyl groups retarded the oxidation process under these reaction conditions. The chemistry of the 1,4‐dione is then explored through reduction and condensation reactions. In two examples, reaction of the 1,4‐dione with diamines gives an unusual, ring‐contracted product 20, which has a high quantum yield. Additionally, the 1,4‐dione can be converted into larger heterocycles such as 21 and 22 featuring an isoquinoline core. The 1,4‐diones and their products have been investigated by spectroscopy, cyclic voltammetry, theoretical studies, and X‐ray crystallography. The results obtained demonstrate the potential of the 1,4‐dione to serve as an invaluable precursor for NDI‐based research.
Settle It Twice: How to Use a Pending Summary Judgment Motion in Mediation
Authors: Young Michael D.
Published: February 2016

Don't you just love it? Your employment case is in the discovery stage when the defense suggests an early mediation. No promises, of course, but the defendant thinks it would be a “productive exercise” to see if the parties can find a settlement before the litigation fees and costs get too far out of control.
Synthesis and Dynamics of Nanosized Phenylene–Ethynylene–Butadiynylene Rotaxanes and the Role of Shape Persistence
Authors: Schweez Christopher , Shushkov Philip , Grimme Stefan , Höger Sigurd
Published: February 2016

Phenylacetylene‐based [2]rotaxanes were synthesized by a covalent‐template approach by aminolysis of the corresponding prerotaxanes. The wheel and the bulky stoppers are made of phenylene–ethynylene–butadiynylene macrocycles of the same size. The stoppers are large enough to enable the synthesis and purification of the rotaxane. However, the wheel unthreads from the axle at elevated temperatures. The deslipping kinetics and the activation parameters were determined. We described theoretically the unthreading by state‐of‐the‐art DFT‐based molecular‐mechanics models and a string method for the simulation of rare events. This approach enabled us to characterize in detail the unthreading mechanism, which involves the folding of the stopper during its passage through the wheel opening, a process that defies intuitive geometrical considerations. The conformational and energetic features of the transition allowed us to infer the molecular residues controlling the disassembly timescale.
Drug Repurposing Identifies Inhibitors of Oseltamivir‐Resistant Influenza Viruses
Authors: Bao Ju , Marathe Bindumadhav , Govorkova Elena A. , Zheng Jie J.
Published: February 2016

The neuraminidase (NA) inhibitor, oseltamivir, is a widely used anti‐influenza drug. However, oseltamivir‐resistant H1N1 influenza viruses carrying the H275Y NA mutation spontaneously emerged as a result of natural genetic drift and drug treatment. Because H275Y and other potential mutations may generate a future pandemic influenza strain that is oseltamivir‐resistant, alternative therapy options are needed. Herein, we show that a structure‐based computational method can be used to identify existing drugs that inhibit resistant viruses, thereby providing a first line of pharmaceutical defense against this possible scenario. We identified two drugs, nalidixic acid and dorzolamide, that potently inhibit the NA activity of oseltamivir‐resistant H1N1 viruses with the H275Y NA mutation at very low concentrations, but have no effect on wild‐type H1N1 NA even at a much higher concentration, suggesting that the oseltamivir‐resistance mutation itself caused susceptibility to these drugs.
Stereoselective Halogenation in Natural Product Synthesis
Authors: Chung Won‐jin , Vanderwal Christopher D.
Published: February 2016

At last count, nearly 5000 halogenated natural products have been discovered. In approximately half of these compounds, the carbon atom to which the halogen is bound is sp3‐hybridized; therefore, there are an enormous number of natural products for which stereocontrolled halogenation must be a critical component of any synthesis strategy. In this Review, we critically discuss the methods and strategies used for stereoselective introduction of halogen atoms in the context of natural product synthesis. Using the successes of the past, we also attempt to identify gaps in our synthesis technology that would aid the synthesis of halogenated natural products, as well as existing methods that have not yet seen application in complex molecule synthesis. The chemistry described herein demonstrates yet again how natural products continue to provide the inspiration for critical advances in chemical synthesis.
Hexasubstituted Benzenes with Ultrastrong Dipole Moments
Authors: Wudarczyk Jakob , Papamokos George , Margaritis Vasilis , Schollmeyer Dieter , Hinkel Felix , Baumgarten Martin , Floudas George , Müllen Klaus
Published: February 2016

Hexasubstituted benzenes have been synthesized with the highest known dipole moments, as determined by dielectric spectroscopy and DFT methods. Based on the preparation of 4,5‐diamino‐3,6‐dibromophthalonitrile, combined with a novel method to synthesize dihydrobenzimidazoles, these benzene derivatives have dipole moments in excess of 10 debye. Such dipole moments are desirable in ferroelectrics, nonlinear optics, and in organic photovoltaics. Structure determination was achieved through single‐crystal X‐ray crystallography, and the optical properties were determined by UV/Vis absorption and fluorescence spectroscopy.
Bipyridinium Polymers That Dock Tetrathiafulvalene Guests in Water Driven by Donor–Acceptor and Ion Pair Interactions
Authors: Zhang Yun‐Chang , Qin Ying , Wang Hui , Zhang Dan‐Wei , Yang Guanyu , Li Zhan‐Ting
Published: February 2016

Two water‐soluble para‐xylylene‐connected 4,4′‐bipyridinium (BIPY2+) polymers have been prepared. UV‐Vis absorption, 1H NMR spectroscopy, and cyclic voltammetry experiments support that in water the BIPY2+ units in the polymers form stable 1:1 charge‐transfer complexes with tetrathiafulvalene (TTF) guests that bear two or four carboxylate groups. These charge‐transfer complexes are stabilized by the donor–acceptor interaction between electron‐rich TTF and electron‐deficient BIPY2+ units and electrostatic attraction between the dicationic BIPY2+ units and the anionic carboxylate groups attached to the TTF core. On the basis of UV‐Vis experiments, a lower limit to the apparent association constant of the TTF⋅BIPY2+ complexes of the mixtures, 1.8×106 m−1, has been estimated in water. Control experiments reveal substantially reduced binding ability of the neutral TTF di‐ and tetracarboxylic acids to the BIPY2+ molecules and polymers. Moreover, the stability of the charge‐transfer complexes formed by the BIPY2+ units of the polymers are considerably higher than that of the complexes formed between two monomeric BIPY2+ controls and the dicarboxylate‐TTF donor; this has been attributed to the mutually strengthened electron‐deficient nature of the BIPY2+ units of the polymers due to the electron‐withdrawing effect of the BIPY2+ units.
Historische Eisenbahnhubbrücken in Deutschland
Authors: Braun Michael
Published: February 2016

In diesem Beitrag soll über drei Beispiele noch bestehender Hubbrücken für die Eisenbahn berichtet werden. Aus den 1930er‐Jahren stammend, repräsentieren sie einen sehr gehobenen Stand ingenieurtechnischer Leistung in Deutschland. Aus verschiedenen Gründen für den ursprünglichen Zweck nicht mehr benötigt, bedürfen sie dringend der Unterschutzstellung.

Historical railway lift bridges in Germany

In the article below reports on three examples of existing lift bridges for railway purpose. They date from the 1930s and demonstrate a very high level of engineering performance. Because of different reasons they are no longer required and now need protection.
Other species in the aqueous environment of a peptide can invert its intrinsic solvated polyproline II/beta propensity: Implications for amyloid formation
Authors: Mirkin Noemi G. , Krimm Samuel
Published: February 2016

As we have previously shown, the predominance of the polyproline II conformation in the circular dichroism spectra of aqueous polypeptides is related to its lower energy than that of the beta conformation. To test whether this is still the case in the presence of additional components in the medium, we have calculated the energy difference between these two conformations in an alanine‐dipeptide/12‐water system without and with the addition of an HCl molecule. We find in the latter case that the beta conformer is of lower energy than the polyproline II. Energy profiles near the minima in both cases also permit conclusions about the relative entropies of these structures. These results emphasize the importance of considering the peptide‐plus‐medium state as the relevant entity in determining the structural properties of such systems. Such an inversion could be relevant to the formation of amyloid and could thus lead to new strategies for studying its role in the development of neurodegenerative diseases. © 2016 Wiley Periodicals, Inc. Biopolymers 105: 305–311, 2016.
Patient‐derived xenograft mouse models of pseudomyxoma peritonei recapitulate the human inflammatory tumor microenvironment
Authors: Kuracha Murali R. , Thomas Peter , Loggie Brian W. , Govindarajan Venkatesh
Published: February 2016

Pseudomyxoma peritonei (PMP) is a neoplastic syndrome characterized by peritoneal tumor implants with copious mucinous ascites. The standard of care for PMP patients is aggressive cytoreductive surgery performed in conjunction with heated intraperitoneal chemotherapy. Not all patients are candidates for these procedures and a majority of the patients will have recurrent disease. In addition to secreted mucin, inflammation and fibrosis are central to PMP pathogenesis but the molecular processes that regulate tumor‐stromal interactions within the peritoneal tumor microenvironment remain largely unknown. This knowledge is critical not only to elucidate PMP pathobiology but also to identify novel targets for therapy. Here, we report the generation of patient‐derived xenograft (PDX) mouse models for PMP and assess the ability of these models to replicate the inflammatory peritoneal microenvironment of human PMP patients. PDX mouse models of low‐ and high‐grade PMP were generated and were of a similar histopathology as human PMP. Cytokines previously shown to be elevated in human PMP were also elevated in PDX ascites. Significant differences in IL‐6 and IL‐8/KC/MIP2 were seen between human and PDX ascites. Interestingly, these cytokines were mostly secreted by mouse‐derived, tumor‐associated stromal cells rather than by human‐derived PMP tumor cells. Our data suggest that the PMP PDX mouse models are especially suited to the study of tumor‐stromal interactions that regulate the peritoneal inflammatory environment in PMP as the tumor and stromal cells in these mouse models are of human and murine origins, respectively. These mouse models are therefore, likely to be useful in vivo surrogates for testing and developing novel therapeutic treatment interventions for PMP.
Nitrogen‐Doped Foam‐like Carbon Plate Consisting of Carbon Tubes as High‐Performance Electrode Materials for Supercapacitors
Authors: Dong Yinghu , Wang Wenxiu , Quan Hongying , Huang Zhongning , Chen Dezhi , Guo Lin
Published: February 2016

A nitrogen‐doped foam‐like 3D carbon plate is prepared by carbonizing a selected biomass precursor of pomelo peel. The carbon plate is composed of interwoven connected carbon tubes and shows a unique 3D interpenetrating macroporous network with binary‐channel structure. Owing to the proper pore structures, short ion‐diffusion paths, high conductivity, and high structure stability, the carbon plate exhibits excellent electrochemical performance as an electrode for supercapacitors directly. A high specific capacitance of up to 338 F g−1 at 1 A g−1, good rate capability with a capacitance retention of 59 % at 20 A g−1, and high cycling stability with only 4 % capacitance loss after 5000 cycles at 20 A g−1 can be achieved in 6 m KOH electrolyte in a three‐electrode system. Furthermore, a symmetric supercapacitor fabricated by using the carbon plates delivers an energy density of 11.05 Wh kg−1 at a power density of 250 W kg−1, and an outstanding cycling stability with only 2.4 % capacitance decay over 5000 cycles at 5 A g−1 in 6 m KOH electrolyte. These very attractive electrochemical properties indicate that the carbon plate derived from pomelo peel is a promising electrode material for supercapacitors.
Interaction Study and Reactivity of ZrIV‐Substituted Wells–Dawson Polyoxometalate towards Hydrolysis of Peptide Bonds in Surfactant Solutions
Authors: Quanten Thomas , Shestakova Pavletta , Van Den Bulck Dries , Kirschhock Christine , Parac‐Vogt Tatjana N.
Published: February 2016

The interaction between the 1:2 ZrIV:Wells–Dawson complex, K15H[Zr(α2‐P2W17O61)2] (1), and a range of surfactants was studied in detail with the aim of developing metal‐substituted POMs as potential artificial proteases for membrane proteins. The surfactants include the positively charged cetyl(trimethyl)ammonium bromide (CTAB), the negatively charged sodium dodecyl sulfate (SDS), the neutral Triton X‐100 (TX‐100), and zwitterionic 3‐[dodecyl(dimethyl)ammonio]‐1‐propanesulfonate (Zw3‐13) and 3‐[dimethyl(3‐{[(3α,5β,7α,12α)‐3,7,12‐trihydroxy‐24‐oxocholan‐24‐yl]amino}propyl)ammonio]‐1‐propanesulfonate (CHAPS). A combination of multinuclear 1H, 13C, and 31P NMR spectroscopy, 1H diffusion‐ordered NMR spectroscopy (1H DOSY), and nuclear Overhauser effect spectroscopy (NOESY) was used to examine the interaction between 1 and each surfactant on the molecular level. Cationic surfactant CTAB caused precipitation of 1 due to strong electrostatic interactions, while the anionic SDS and neutral TX‐100 surfactants did not exhibit any interaction at neutral pD. 1H DOSY NMR spectroscopy indicated an interaction between 1 and zwitterionic surfactants Zw3‐12 and CHAPS, which occurs via the positively charged ammonium group in the surfactant molecule. In the presence of anionic, neutral, and zwitterionic surfactants, 1 preserves its catalytic activity towards the hydrolysis of the peptide bond in the dipeptide glycyl‐l‐histidine (GH). The fastest hydrolysis was observed at pD 7.0 and could be rationalized by taking into account pD‐dependent speciation of 1 and coordination properties of GH.
Stable Crystalline Forms of Na Polysulfides: Experiment versus Ab Initio Computational Prediction
Authors: Mali Gregor , Patel Manu U. M. , Mazaj Matjaž , Dominko Robert
Published: February 2016

For the design of light‐metal–sulfur batteries and for the understanding of their performance, knowledge on the stable crystalline polysulfides is very important. We confronted experimental and ab initio crystal structure prediction studies on the stability of Na polysulfides. The selected evolutionary‐based structure‐prediction algorithm was able to quickly and correctly predict the thermodynamically stable crystalline forms of Na polysulfides with small unit cells. For Na polysulfides with large unit cells, the algorithm correctly proposed short unbranched polysulfide chains to be energetically favorite structural motifs, but could not find proper three‐dimensional structures in the limited number of generations. Experimentally, the polysulfides were studied by X‐ray diffraction and 23Na solid‐state NMR spectroscopy. Complemented by calculations of the isotropic chemical shifts and quadrupolar coupling constants, NMR spectroscopy proved to be an excellent tool for the examination of Na polysulfides, because it allowed easy distinction and quantification of components in the samples.
A Supramolecular Chiral Auxiliary Approach: “Remote Control” of Stereochemistry at a Hierarchically Assembled Dimeric Helicate
Authors: Van Craen David , Albrecht Markus , Raabe Gerhard , Pan Fangfang , Rissanen Kari
Published: February 2016

Dimeric hierarchically‐assembled titanium(IV) helicates are in solvent‐dependent equilibrium with the corresponding monomers. Statistically formed mixtures of such complexes bearing chiral stereocontrolling ligands and achiral diene‐substituted ligands show high diastereoselectivity and reasonable enantioselectivity in the Diels–Alder reaction with maleimides if the reaction proceeds with the dimer but not with the monomer. Thus, solvent dependent switching between the monomer and dimer enables on/off switching of the enantioselectivity.
Synthesis of Triarylpyridines in Thiopeptide Antibiotics by Using a C−H Arylation/Ring‐Transformation Strategy
Authors: Amaike Kazuma , Itami Kenichiro , Yamaguchi Junichiro
Published: February 2016

We have described a C−H arylation/ring‐transformation strategy for the synthesis of triarylpyridines, which form the core structure of thiopeptide antibiotics. This synthetic method readily gave 2,3,6‐triarylpyridines in a regioselective manner by a two‐phase approach: C−H arylation (a nickel‐catalyzed decarbonylative Suzuki–Miyaura cross‐coupling and decarbonylative C−H coupling for the synthesis of 2,4‐diaryloxazoles) and ring transformation ([4+2] cycloaddition of 2,4‐diaryloxazoles with (hetero)arylacrylic acids). To showcase these methods, we have accomplished the formal synthesis of thiopeptide antibiotics GE2270 s and amythiamicins.
Platinum‐Catalyzed Friedel–Crafts‐Type C−H Coupling–Allylic Amination Cascade to Synthesize 3,4‐Fused Tricyclic Indoles
Authors: Suzuki Yuta , Tanaka Yuito , Nakano Shun‐ichi , Dodo Kosuke , Yoda Natsumi , Shinohara Ken‐ichi , Kita Kazuko , Kaneda Atsushi , Sodeoka Mikiko , Hamada Yasumasa , Nemoto Tetsuhiro
Published: February 2016

A novel platinum‐catalyzed cascade cyclization reaction was developed by intramolecular Friedel–Crafts‐type C−H coupling of aniline derivatives with a propargyl carbonate unit‐allylic amination sequence. Treatment of various propargyl carbonates tethered to meta‐aniline derivatives with a Pt(dba)3/DPEphos catalyst system afforded the corresponding 3,4‐fused tricyclic 3‐alkylidene indolines in 42–99 % yield, which were transformed into 3,4‐fused indole derivatives by reaction with trifluoroacetic acid. The reaction products exhibited antiproliferative activities against cancer cells, but not normal cells, revealing the potential usefulness of this reaction for medicinal chemistry.
To Tattoo or not to Tattoo
Authors: Petersen Henrik , Roth Klaus
Published: February 2016

Tätowierungen sind ein häufig geschätzter, häufig verdammter Teil unseres kulturellen Erbes. In den letzten Jahrzehnten war ein erstaunliches Comeback zu beobachten. Tätowierungen wurden Mode und heute haben etwa 100 Millionen Europäer mindestens eine Tätowierung. Den meisten Trägern sind weder die damit verbundenen gesundheitlichen Risiken noch die teilweise bestehenden Mängel in der Ausbildung der Tätowierer, den hygienischen Arbeitsbedingungen und der Qualität der verwendeten Farben bewusst. Um den ganzen Tätowierungsprozess kritisch bewerten zu können, wird die Einbringung und das Schicksal der Farben in der Haut eines Tätowierten aus chemischer Sicht analysiert.
Der Unterwasser‐Klebstoff der Muscheln
Authors: Groß Michael
Published: February 2016

Durch systematische Variation einer bakteriellen Substanz, die einem klebrigen Protein der Muscheln ähnelt, konnten Forscher aufklären, unter welchen Voraussetzungen ein biologischer Klebstoff im Meerwasser funktionieren kann.
Leistungsfähige Materialien und Ressourcen‐effiziente Lösungen sind gefragt
Authors: Schubert Ulrich
Published: February 2016

Die Auffächerung der Chemie in Teilgebiete ist in den vergangenen Jahrzehnten sehr breit geworden und reflektiert unter anderem die zunehmende Wechselwirkung mit angrenzenden Gebieten aus Wissenschaft und Technik. Diese Entwicklung birgt aber auch die große Gefahr in sich, dass sich “chemische Subkulturen” bilden, die untereinander den Kontakt verlieren. Eine Rückbesinnung an das gemeinsame Zentrum hat nichts mit Nostalgie zu tun, sondern ist vonnöten um den spezifischen Denkweisen der Chemie und deren Herangehensweisen zur Lösung von Problemen Geltung zu verschaffen. Hier hat Chemie in unserer Zeit eine wichtige Funktion, vermittelt sie doch, unter Verzicht auf “Fachchinesisch”, Nicht‐Spezialisten grundlegende Einblicke in die einzelnen Unter‐Disziplinen.
Das Genom
Authors: Groß Michael
Published: February 2016

15 Jahre nach der Erstsequenzierung des menschlichen Genoms wissen wir, dass es weit weniger Gene gibt als erwartet, und dass die Gensequenzen im Humangenom nicht die Antworten auf die offenen Fragen der Medizin liefern. Das hat die Aufmerksamkeit auf komplexe Zusammenhänge im Umfeld der Gene gelenkt, wie regulatorische Elemente, Stichwort Epigenetik, und die ehemalige Junk‐DNA, die keineswegs Müll ist, sondern auf komplexe und unerwartete Weise mit vielfältigen Funktionen der Zelle wechselwirkt. In dieser Serie werden deshalb die Komplexität und Netzwerk‐Eigenschaft der Chemie des Lebens im Mittelpunkt stehen. In jeder Ausgabe wollen wir einen Knotenpunkt des Netzwerks näher betrachten und dann erkennen, wie dieser mit anderen Funktionen zusammenhängt.
Natural yellow and red Fe‐based geomaterials from the Lessini mountains in Veneto, Italy: A review
Authors: Cavallo Giovanni , Riccardi Maria Pia , Zorzin Roberto
Published: February 2016

The possibility that natural earths from Lessini Mountains were used in archaeological and artistic contexts is an intriguing question; nevertheless, a first attempt in provenance studies was made only recently. This contribution discusses critically the bibliographic records following a chronological perspective in the light of the most recent scientific research in order to propose the state of the art on the evolution of the knowledge of yellow and red earths in the Western sector of the Lessini Mountains. © 2016 Wiley Periodicals, Inc. Col Res Appl, 41, 221–225, 2016
Kinetics of Reactive Modules Adds Discriminative Dimensions for Selective Cell Imaging
Authors: Quérard Jérôme , Le Saux Thomas , Gautier Arnaud , Alcor Damien , Croquette Vincent , Lemarchand Annie , Gosse Charlie , Jullien Ludovic
Published: February 2016

Living cells are chemical mixtures of exceptional interest and significance, whose investigation requires the development of powerful analytical tools fulfilling the demanding constraints resulting from their singular features. In particular, multiplexed observation of a large number of molecular targets with high spatiotemporal resolution appears highly desirable. One attractive road to address this analytical challenge relies on engaging the targets in reactions and exploiting the rich kinetic signature of the resulting reactive module, which originates from its topology and its rate constants. This review explores the various facets of this promising strategy. We first emphasize the singularity of the content of a living cell as a chemical mixture and suggest that its multiplexed observation is significant and timely. Then, we show that exploiting the kinetics of analytical processes is relevant to selectively detect a given analyte: upon perturbing the system, the kinetic window associated to response read‐out has to be matched with that of the targeted reactive module. Eventually, we introduce the state‐of‐the‐art of cell imaging exploiting protocols based on reaction kinetics and draw some promising perspectives.
Faster acquisition of symbiotic partner by common mycorrhizal networks in early plant life stage
Authors: Varga Sandra , Kytöviita Minna‐Maarit
Published: February 2016

Arbuscular mycorrhizal (AM) fungi usually improve plant performance yet our knowledge about their effects on seed germination and early plant establishment is very limited. We performed a factorial greenhouse experiment where the seeds from four low Arctic co‐occurring mycorrhizal herbs (Antennaria dioica, Campanula rotundifolia, Sibbaldia procumbens, and Solidago virgaurea) were germinated alone or in the vicinity of an adult Sibbaldia plant with or without AM fungi; given either as spores or being present in a common mycorrhizal network (CMN). Three different AM fungal species were examined to assess species‐specific differences in symbiont acquisition rate. Of the four plant species investigated, the presence of AM fungi affected seed germination only in Campanula and this effect was dependent on whether the AM fungi were present in the soil as spores or as a CMN. Overall, after germination, developing seedlings showed AM fungal colonization in their roots as soon as 2 d after cotyledon emergence. Our results show that CMN may provide germinating seedlings faster acquisition of the AM fungal partner in comparison to acquisition from spores. Furthermore, there were AM species‐specific differences in the symbiont acquisition rate highlighting the importance of species identity in AM interactions. These findings suggest that while AM fungi may not play a fundamental role during seed germination, plant community composition may be affected by the species‐specific AM fungal effects on seedling establishment and CMN acquisition.
Two Green‐Phosphorescent Iridium Complexes with 2‐Phenylpyrimidine Derivatives and Tetraphenylimidodiphosphinate for Efficient Organic Light‐Emitting Diodes
Authors: Zhang Song , Xia Jing‐Cheng , Wu Zheng‐Guang , Lu Guang‐Zhao , Zhao Yue , Zheng You‐Xuan
Published: February 2016

Two phosphorescent IrIII complexes Ir1 and Ir2 containing 5‐fluoro‐2‐[4‐(trifluoromethyl)phenyl]pyrimidine and 2‐(3,4‐difluorophenyl)‐5‐fluoropyrimidine as cyclometalated main ligand and tetraphenylimidodiphosphinate as ancillary ligand were synthesized. Ir1 was characterized by single‐crystal X‐ray crystallography. Ir1 and Ir2 show green emissions peaking at 527 and 513 nm, respectively. By using the two complexes as emitters, organic light‐emitting diodes (OLEDs) with the structure of TAPC (1,1‐bis[4‐(di‐p‐tolylamino)phenyl]cyclohexane, 40 nm)/Ir1 or Ir2 (10 wt.‐%):mCP (1,3‐bis(9H‐carbazol‐9‐yl)benzene, 20 nm)/TmPyPB (1,3,5‐tris(m‐pyrid‐3‐ylphenyl)benzene, 30 nm)/LiF (1 nm)/Al (100 nm) showed high performance with maximum current efficiencies as high as 81.91 or 71.17 cd A–1 and maximum external quantum efficiencies of 20.8 or 21.3 %, respectively. The low‐efficiency roll‐off ratios of the two devices suggest that the two complexes have potential applications in OLEDs.
Influence of mineral admixtures on mechanical properties of self‐compacting concrete under elevated temperature
Authors: N Anand , I Antony Godwin , G Prince Arulraj
Published: February 2016

Self‐compacting concrete (SCC) is a form of concrete that is capable of flowing into the congested interior of formwork and consolidating under the action of its own weight without segregation and bleeding. In the present investigation, an attempt has been made to study the effect of elevated temperature on mechanical properties of SCC specimens made with different mineral admixtures that were heated from 27 to 900 °C and cooled by air or water. Silica fume, flyash, metakaolin were used as mineral admixtures. Master Glenium was used as superplasticizer, and Glenium Stream 2 was used as viscosity modifying agent. Mechanical properties of the cooled specimens such as compressive strength, tensile strength, flexural strength, and modulus of elasticity were found. Compressive, tensile, and flexural strengths of specimens were found to decrease by 73.18%, 65.05%, and 63.2%, and 85.2%, 83.52%, and 83.56% for the specimens with metakaolin that were heated and cooled by air and water, respectively. Similar reductions were found for the SCC specimens made with silica fume and flyash. Microstructure investigation has been carried out on SCC samples using scanning electron microscope and X‐ray diffraction analytical techniques to understand the effect of temperature on decrease in strength. Copyright © 2016 John Wiley & Sons, Ltd.
A change in social activity affect cognitive function in middle‐aged and older Koreans: analysis of a Korean longitudinal study on aging (2006–2012)
Authors: Choi Young , Park Sohee , Cho Kyoung Hee , Chun Sung‐Youn , Park Eun‐Cheol
Published: February 2016

Objective

To examine the association between a changes in social activity and cognitive function in Koreans aged 45 years or older.

Methods

Data were obtained from 6076 participants aged 45 years and older included in the Korean Longitudinal Study of Aging (2006–2012). Cognitive function was measured using the mini‐mental state examination—Korean version (MMSE‐K). Participation in social activities was classified as “consistent participation,” “consistent non‐participation,” “participation to non‐participation,” and “non‐participation to participation.” Linear mixed models were used to investigate the relationship between type of social activity (religious organizations, friendship organizations, leisure/culture/sports clubs, family or school reunion, volunteering work, and political organizations), and cognitive function.

Results

Individuals who reported “no participation to participation” (b = 0.778, p < 0.0001) and “consistent participation” (b = 0.968, p < 0.0001) were more likely to show reduced cognitive decline than those who reported “consistent non‐participation” (p < 0.0001 for trend). The positive association between cognitive function and consistent participation in religious activities, friendship organizations, and family/school reunions was particularly strong (b = 0.325, p < 0.0001; b = 0.570, p < 0.0001; b = 0.234, p = 0.0004; respectively, versus consistent non‐participation).

Conclusions

Promotion of participation in religious organizations, friendship organizations, and family/school reunions (only for older persons) may help preserve cognitive function in individuals aged 45 years or older in Korea. Copyright © 2016 John Wiley & Sons, Ltd.
Structural brain correlates of cognitive and behavioral impairment in MND
Authors: Agosta Federica , Ferraro Pilar M. , Riva Nilo , Spinelli Edoardo G. , Chiò Adriano , Canu Elisa , Valsasina Paola , Lunetta Christian , Iannaccone Sandro , Copetti Massimiliano , Prudente Evelina , Comi Giancarlo , Falini Andrea , Filippi Massimo
Published: February 2016

Objective

To assess the structural correlates of cognitive and behavioral impairment in motor neuron diseases (MND) using multimodal MRI.

Methods

One hundred one patients with sporadic MND (56 classic amyotrophic lateral sclerosis, 31 upper motor neuron phenotype, and 14 lower motor neuron phenotype) and 51 controls were enrolled. Patients were classified into MND with a pure motor syndrome (MND‐motor) and with cognitive/behavioral symptoms (MND‐plus). Cortical thickness measures and diffusion tensor (DT) metrics of white matter (WM) tracts were assessed. A random forest approach was used to explore the independent role of cortical and WM abnormalities in explaining major cognitive and behavioral symptoms.

Results

There were 48 MND‐motor and 53 MND‐plus patients. Relative to controls, both patient groups showed a distributed cortical thinning of the bilateral precentral gyrus, insular and cingulate cortices, and frontotemporal regions. In all regions, there was a trend toward a more severe involvement in MND‐plus cases, particularly in the temporal lobes. Both patient groups showed damage to the motor callosal fibers, which was more severe in MND‐plus. MND‐plus patients also showed a more severe involvement of the extra‐motor WM tracts. The best predictors of executive and non‐executive deficits and behavioral symptoms in MND were diffusivity abnormalities of the corpus callosum and frontotemporal tracts, including the uncinate, cingulum, and superior longitudinal fasciculi.

Conclusions

Cortical thinning and WM degeneration are highly associated with neuropsychological and behavioral symptoms in patients with MND. DT MRI metrics seem to be the most sensitive markers of extra‐motor deficits within the MND spectrum. Hum Brain Mapp 37:1614‐1626, 2016. © 2016 Wiley Periodicals, Inc.
Indications, reconstructive techniques, and results for total glossectomy
Authors: Mazarro Alejandro , de Pablo Alba , Puiggròs Carolina , Velasco Mª Mercedes , Saez Manel , Pamias Jorge , Bescós Coro
Published: February 2016

Background

The best treatment for advanced tongue tumors remains controversial. Total glossectomy with laryngeal preservation is considered a feasible option, despite its morbidity.

Methods

A retrospective analysis of 12 total glossectomies with laryngeal preservation was performed in order to assess the available reconstruction techniques and analyze survival and functional outcomes.

Results

One‐year overall survival (OS) and disease‐free survival (DFS) rates were 58.3% and 33.3%, respectively, both dropping to 25% after 3 years. Permanent gastrostomy was necessary in 10 patients, although videofluoroscopy revealed adequate tolerance to liquids. Speech intelligibility was satisfactory in 50% of the patients and severely impaired in the remaining 50%.

Conclusion

Laryngeal preservation in the context of advanced tumors of the tongue without supraglottic invasion carried similar oncologic results to total glossectomy with laryngectomy, but offers a better phonatory function. However, it is usually associated with a higher gastrostomy dependency ratio. A scrupulous selection of candidates is mandatory. © 2016 Wiley Periodicals, Inc. Head Neck 38: E2004–E2010, 2016
A genetic algorithm encoded with the structural information of amino acids and dipeptides for efficient conformational searches of oligopeptides
Authors: Ru Xiao , Song Ce , Lin Zijing
Published: February 2016

The genetic algorithm (GA) is an intelligent approach for finding minima in a highly dimensional parametric space. However, the success of GA searches for low energy conformations of biomolecules is rather limited so far. Herein an improved GA scheme is proposed for the conformational search of oligopeptides. A systematic analysis of the backbone dihedral angles of conformations of amino acids (AAs) and dipeptides is performed. The structural information is used to design a new encoding scheme to improve the efficiency of GA search. Local geometry optimizations based on the energy calculations by the density functional theory are employed to safeguard the quality and reliability of the GA structures. The GA scheme is applied to the conformational searches of Lys, Arg, Met‐Gly, Lys‐Gly, and Phe‐Gly‐Gly representative of AAs, dipeptides, and tripeptides with complicated side chains. Comparison with the best literature results shows that the new GA method is both highly efficient and reliable by providing the most complete set of the low energy conformations. Moreover, the computational cost of the GA method increases only moderately with the complexity of the molecule. The GA scheme is valuable for the study of the conformations and properties of oligopeptides. © 2016 Wiley Periodicals, Inc.