bluuebunny/crossref_metadata_2025 huggingface dataset:
The Influence of Hemicellulose Sugars on Product Distribution of Early‐Stage Conversion of Lignin Oligomers Catalysed by Raney Nickel
Authors: Chesi Claudio , de Castro Ilton B. D. , Clough Matthew T. , Ferrini Paola , Rinaldi Roberto
Published: May 2016

We recently introduced catalytic upstream biorefining, a fractionation process performed on whole lignocellulosic materials, based on the early‐stage conversion of lignin by hydrogen‐transfer reactions (using Raney Ni as the catalyst and 2‐PrOH as a hydrogen‐donor). The process fractionates lignocellulose, isolating lignin as an extensively depolymerised oil, opening up new avenues in the catalytic upgrading of bio‐derived phenolic streams to chemicals and fuels. In addition, highly delignified holocellulose pulps are obtained, holding potential as a feedstock for the production of paper, chemicals, and biofuels. Herein, we report our first results on the chemistry underlying this process under nearly neutral to slightly alkaline conditions achieved by the addition of inorganic bases. This report sheds light on the influence of hemicellulose sugars on the product distribution obtained from the early‐stage catalytic conversion of lignin oligomers released from lignocellulose. The increase in the pH value of the medium suppressed the hydrolysis of xylans. As a result, a dramatic increase in the xylans retention from 10 % (at pH 4.5) up to 60 % (at pH>7.5) was achieved. Interestingly, the pH value of the liquor did not affect the delignification extent of lignocellulose or the absolute content of glucans retained in the holocellulose. By enhancing xylans retention, we provide evidence that hemicellulose sugars decrease the activity of Raney Ni towards full hydrogenation of the aromatic species composing the lignin stream. In fact, the yield of selected cyclohexanols increases from 0.8 % (no added bases) to 4.4 % (added NaOH), whereas the yield of selected phenols decreases from 12.9 % (no added bases) to 7.2 % (added NaOH).
Study of Lanthanum Manganate and Yttrium‐Stabilized Zirconia‐Supported Palladium Dual‐Bed Catalyst System for the Total Oxidation of Methane: A Study by 18O2/16O2 Isotopic Exchange
Authors: Richard Mélissandre , Can Fabien , Gil Sonia , Giroir‐Fendler Anne , Duprez Daniel , Bion Nicolas
Published: May 2016

The front cover artwork for Issue 11/2016 is provided by researchers from IC2MP (University of Poitiers, CNRS) and IRCELYON (University of Lyon 1, CNRS). The image shows the enhancement of the methane oxidation activity on yttrium‐stabilized zirconia‐supported palladium implied by the exchange process occurring between gaseous oxygen and lattice oxygen atoms from lanthanum manganate. See the Full Paper itself at http://dx.doi.org/10.1002/cctc.201501398.
Per‐Substituted [8]Circulene and Its Non‐Planar Fragments: Synthesis, Structural Analysis, and Properties
Authors: Feng Chieh‐Ning , Hsu Wen‐Ching , Li Jen‐Yi , Kuo Ming‐Yu , Wu Yao‐Ting
Published: May 2016

The syntheses, structures, and physical properties of a full series of benzannulated tetraphenylenes are reported. The palladium‐catalyzed annulation of tetraiodo‐substituted 2,3,6,7,10,11,14,15‐octamethyltetraphenylene with insufficient di(4‐anisyl)ethyne yielded a mixture of per‐substituted [8]circulene and its non‐planar fragments, including mono‐, para‐di‐, ortho‐di‐, and triannulated products. Their structures were unambiguously verified by X‐ray crystallography. Successive benzannulations significantly affect the molecular geometries, dynamic behaviors, and physical properties of the compounds. In this series of compounds, [8]circulene is the most strained one, as reflected by the significant deplanarization of the phenanthrene moieties (ca. 63° in the bay region) and the fact that it has the highest strain energy (120.6 kcal mol−1). The dynamic behaviors of these compounds were examined both experimentally and theoretically. The ring flipping of per‐substituted [8]circulene is confirmed to proceed through pseudorotation with a barrier of around 21 kcal mol−1, whereas its non‐planar fragments require much more energy for the ring inversion. The photophysical and electrochemical properties of the investigated compounds depend strongly on the extent of efficient π conjugation. The successive benzannulations red‐shift both the absorption and the emission bands, and reduce the first oxidation potential.
Helicenes as All‐in‐One Organic Materials for Application in OLEDs: Synthesis and Diverse Applications of Carbo‐ and Aza[5]helical Diamines
Authors: Jhulki Samik , Mishra Abhaya Kumar , Chow Tahsin J. , Moorthy Jarugu Narasimha
Published: May 2016

A set of eight helical diamines were designed and synthesized to demonstrate their relevance as all‐in‐one materials for multifarious applications in organic light‐emitting diodes (OLEDs), that is, as hole‐transporting materials (HTMs), EMs, bifunctional hole transporting + emissive materials, and host materials. Azahelical diamines function very well as HTMs. Indeed, with high Tg values (127–214 °C), they are superior alternatives to popular N,N′‐di(1‐naphthyl)‐N,N′‐diphenyl‐(1,1′‐biphenyl)‐4,4′‐diamine (NPB). All the helical diamines exhibit emissive properties when employed in nondoped as well as doped devices, the performance characteristics being superior in the latter. One of the carbohelical diamines (CHTPA) serves the dual function of hole transport as well as emission in simple double‐layer devices; the efficiencies observed were better by quite some margin than those of other emissive helicenes reported. The twisting endows helical diamines with significantly high triplet energies such that they also function as host materials for red and green phosphors, that is, [Ir(btp)2acac] (btp=2‐(2′‐benzothienyl)pyridine; acac=acetylacetonate) and [Ir(ppy)3] (ppy=2‐phenylpyridine), respectively. The results of device fabrications demonstrate how helicity/ helical scaffold may be diligently exploited to create molecular systems for maneuvering diverse applications in OLEDs.
Dependence of Mesomorphic Behaviour of Methylene‐Linked Dimers and the Stability of the NTB/NX Phase upon Choice of Mesogenic Units and Terminal Chain Length
Authors: Mandle Richard J. , Goodby John W.
Published: May 2016

Twelve symmetrical dimeric materials consisting of a nonamethylene (C9) spacer and either phenyl 4‐(4′‐alkylphenyl)benzoate, phenyl 4‐(4′‐alkylcyclohexyl)benzoate or phenyl 4‐(4′‐alkylbicyclohexyl)carboxylate mesogenic units were prepared and their mesogenic behaviour characterised by POM, DSC and XRD. All of the materials exhibited nematic phases with clearing points in excess of 200 °C. Four compounds were found to exhibit the twist‐bend nematic phase, with one material exhibiting a transition from the NTB phase into an anticlinic smectic ‘X’ phase. Across all three series of compounds the length of terminal chain is seen to dictate, to some degree, the type of mesophase formed: shorter terminal chains favour nematic and NTB mesophases, whereas longer terminal aliphatic chains were found to promote smectic phases.
Iron(III)‐Catalyzed Arylation of Spiro‐Epoxyoxindoles with Phenols/Naphthols towards the Synthesis of Spirocyclic Oxindoles
Authors: Luo Mupeng , Yuan Rongju , Liu Xuesong , Yu Linqian , Wei Wanguo
Published: May 2016

An efficient and highly regioselective iron(III)‐catalyzed Friedel–Crafts‐type arylation of spiro‐epoxyoxindoles with phenols was developed for rapid access to 3‐(3‐indolyl)‐oxindole‐3‐methanols, which could be further elaborated into benzofuranyl‐spirooxindoles under Mitsunobu conditions. When spiro‐epoxyoxindoles were reacted with naphthols in the presence of a catalytic amount of FeCl3⋅6 H2O in dichloromethane, they underwent a tandem Friedel–Crafts‐type arylation and O‐cyclization to yield novel naphthofuranyl‐spirooxindoles in excellent yields. This method is applied to enable the efficient and highly regioselective synthesis of a small‐molecule inhibitor of the sodium channel Nav1.7 (±)‐XEN402, which is currently in a phase IIb clinical trial for the treatment of pain.
Enhanced Fluorescence Turn‐on Imaging of Hypochlorous Acid in Living Immune and Cancer Cells
Authors: Mulay Sandip V. , Choi Minsuk , Jang Yoon Jeong , Kim Youngsam , Jon Sangyong , Churchill David G.
Published: May 2016

Two closely related phenyl selenyl based boron‐dipyrromethene (BODIPY) turn‐on fluorescent probes for the detection of hypochlorous acid (HOCl) were synthesized for studies in chemical biology; emission intensity is modulated by a photoinduced electron‐transfer (PET) process. Probe 2 intrinsically shows a negligible background signal; however, after reaction with HOCl, chemical oxidation of selenium forecloses the PET process, which evokes a significant increase in fluorescence intensity. The fluorescence intensity of probes 1 and 2 with HOCl involves an ∼18 and ∼50‐fold enhancement compared with the respective responses from other reactive oxygen/nitrogen species (ROS/RNS) and low detection limits (30.9 nm for 1 and 4.5 nm for 2). Both probes show a very fast response with HOCl; emission intensity reached a maximum within 1 s. These probes show high selectivity for HOCl, as confirmed by confocal microscopy imaging when testing with RAW264.7 and MCF‐7 cells.
Enantiospecific Synthesis and Cytotoxicity Evaluation of Oximidine II Analogues
Authors: Schneider Christopher M. , Li Wei , Khownium Kriangsak , Lushington Gerald H. , Georg Gunda I.
Published: May 2016

Analogues of the anticancer natural product oximidine II were prepared and evaluated for cytotoxicity. One analogue of oximidine II that carries a C15 allylic amide side chain as well as two analogues with C15 vinyl sulfone side chains were found to lack cytotoxicity against the cancer cell line SK‐Mel‐5, thereby confirming the necessity of the C15 enamide side chain of oximidine II for cytotoxicity. Four analogues, designed by comparative molecular similarity index analysis (CoMSIA), that feature a less complex macrolactone scaffold were prepared and tested. The two analogues carrying a C15 vinyl sulfone group and the two analogues with a C15 oximidine II enamide side chain showed weak cytotoxicity against the SK‐Mel‐5 cell line and other cell lines, indicating that the designed simplified macrocycles cannot replace the oximidine II macrocycle.
Codon 13 KRAS mutation predicts patterns of recurrence in patients undergoing hepatectomy for colorectal liver metastases
Authors: Margonis Georgios A. , Kim Yuhree , Sasaki Kazunari , Samaha Mario , Amini Neda , Pawlik Timothy M.
Published: May 2016

BACKGROUND

Investigations regarding the impact of tumor biology after surgical management of colorectal liver metastasis have focused largely on overall survival. We investigated the impact of codon‐specific KRAS mutations on the rates and patterns of recurrence in patients after surgery for colorectal liver metastasis (CRLM).

METHODS

All patients who underwent curative‐intent surgery for CRLM between 2002 and 2015 at Johns Hopkins who had available data on KRAS mutation status were identified. Clinico‐pathologic data, recurrence patterns, and recurrence‐free survival (RFS) were assessed using univariable and multivariable analyses.

RESULTS

A total of 512 patients underwent resection only (83.2%) or resection plus radiofrequency ablation (16.8%). Although 5‐year overall survival was 64.6%, 284 (55.5%) patients recurred with a median RFS time of 18.1 months. The liver was the initial recurrence site for 181 patients, whereas extrahepatic recurrence was observed in 162 patients. Among patients with an extrahepatic recurrence, 102 (63%) had a lung recurrence. Although overall KRAS mutation was not associated with overall RFS (P = 0.186), it was independently associated with a worse extrahepatic (P = 0.004) and lung RFS (P = 0.007). Among patients with known KRAS codon‐specific mutations, patients with codon 13 KRAS mutation had a worse 5‐year extrahepatic RFS (P = 0.01), whereas codon 12 mutations were not associated with extrahepatic (P = 0.11) or lung‐specific recurrence rate (P = 0.24). On multivariable analysis, only codon 13 mutation independently predicted worse overall extrahepatic RFS (P = 0.004) and lung‐specific RFS (P = 0.023).

CONCLUSIONS

Among patients undergoing resection of CRLM, overall KRAS mutation was not associated with RFS. KRAS codon 13 mutations, but not codon 12 mutations, were associated with a higher risk for overall extrahepatic recurrence and lung‐specific recurrence. Cancer 2016. © 2016 American Cancer Society. Cancer 2016;122:2698–2707. © 2016 American Cancer Society.
Distinct subcellular localization of alternative splicing variants of EFA6D, a guanine nucleotide exchange factor for Arf6, in the mouse brain
Authors: Fukaya Masahiro , Ohta Shingo , Hara Yoshinobu , Tamaki Hideaki , Sakagami Hiroyuki
Published: May 2016

EFA6D (guanine nucleotide exchange factor for ADP‐ribosylation factor 6 [Arf6]D) is also known as EFA6R, Psd3, and HCA67. It is the fourth member of the EFA6 family with guanine nucleotide exchange activity for Arf6, a small guanosine triphosphatase (GTPase) that regulates endosomal trafficking and actin cytoskeleton remodeling. We propose a classification and nomenclature of 10 EFA6D variants deposited in the GenBank database as EFA6D1a, 1b, 1c, 1d, 1s, 2a, 2b, 2c, 2d, and 2s based on the combination of N‐terminal and C‐terminal insertions. Polymerase chain reaction analysis showed the expression of all EFA6D variants except for variants a and d in the adult mouse brain. Immunoblotting analysis with novel variant‐specific antibodies showed the endogenous expression of EFA6D1b, EFA6D1c, and EFA6D1s at the protein level, with the highest expression being EFA6D1s, in the brain. Immunoblotting analysis of forebrain subcellular fractions showed the distinct subcellular distribution of EFA6D1b/c and EFA6D1s. The immunohistochemical analysis revealed distinct but overlapping immunoreactive patterns between EFA6D1b/c and EFA6D1s in the mouse brain. In immunoelectron microscopic analyses of the hippocampal CA3 region, EFA6D1b/c was present predominantly in the mossy fiber axons of dentate granule cells, whereas EFA6D1s was present abundantly in the cell bodies, dendritic shafts, and spines of hippocampal pyramidal cells. These results provide the first anatomical evidence suggesting the functional diversity of EFA6D variants, particularly EFA6D1b/c and EFA6D1s, in neurons. J. Comp. Neurol. 524:2531–2552, 2016. © 2016 Wiley Periodicals, Inc.
Hematite Surface Activation by Chemical Addition of Tin Oxide Layer
Authors: Carvalho Waldemir M. , Souza Flavio L.
Published: May 2016

In this study, the effect of tin (Sn4+) modification on the surface of hematite electrodes synthesized by an aqueous solution route at different times (2, 5, 10, 18, and 24 h) is investigated. As confirmed from X‐ray diffraction results, the as‐synthesized electrode exhibits an oxyhydroxide phase, which is converted into a pure hematite phase after being subjected to additional thermal treatment at 750 °C for 30 min. The tin‐modified hematite electrode is prepared by depositing a solution of Sn4+ precursor on the as‐synthesized electrode, followed by thermal treatment under the same abovementioned conditions. This modification results in an enhancement of the photocurrent response for all hematite electrodes investigated and attains the highest values of around 1.62 and 2.3 mA cm−2 at 1.23 and 1.4 V versus RHE, respectively, for electrodes obtained in short synthesis times (2 h). Contact angle measurements suggest that the deposition of Sn4+ on the hematite electrode provides a more hydrophilic surface, which favors a chemical reaction at the interface between the electrode and electrolyte. This result generates new perspectives for understanding the deposition of Sn4+ on the hematite electrode surface, which is in contrast with several studies previously reported; these studies state that the enhancement in photocurrent density is related to either the induction of an increased donor charge density or shift in the flat‐band potential, which favors charge separation.
Fe/Fe3C/N‐Doped Carbon Materials from Metal–Organic Framework Composites as Highly Efficient Oxygen Reduction Reaction Electrocatalysts
Authors: Qian Yuhong , Cavanaugh Jack , Khan Inayat Ali , Wang Xuerui , Peng Yongwu , Hu Zhigang , Wang Yuxiang , Zhao Dan
Published: May 2016

A series of Fe/Fe3C‐containing N‐doped porous carbon materials (Fe/NC) were prepared by pyrolyzing composites that contained a metal–organic framework (MIL‐88c‐Fe) with dicyandiamide. The Fe/NC obtained at 800 °C (Fe/NC800) showed comparable onset potential and kinetics to that of the commercial Pt/C catalyst in catalyzing the oxygen reduction reaction (ORR). Further measurements suggested that it has better durability and much higher methanol tolerance than Pt/C. Acid leaching was performed to reveal the critical role of Fe‐containing sites in ORR catalysis.
Homogeneous Photocatalytic H2 Production Using a RuII Bathophenanthroline Metal‐to‐Ligand Charge‐Transfer Photosensitizer
Authors: Khnayzer Rony S. , Olaiya Babatunde S. , El Roz Karim A. , Castellano Felix N.
Published: May 2016

The prototypical [Ru(bpy)3]2+ (bpy=2,2′‐bipyridine) photosensitizer has been previously demonstrated to be labile in aqueous photocatalytic solutions, especially in the presence of coordinating electron donors. Here, an alternative RuII molecular sensitizer, [Ru(dpp)3]2+ (dpp=4,7‐diphenyl‐1,10‐phenanthroline or bathophenanthroline), is described, which is considerably more stable than its bpy congener, allowing enhanced photocatalysis metrics in conjunction with a cobalt glyoxime ([Co(dmgH)2pyCl], dmgH=dimethylglyoxime, py=pyridine) water reduction catalyst and N,N‐dimethyl‐p‐toluidine (DMT) as the sacrificial donor in a 1:1 mixture of CH3CN/H2O. Photoluminescence studies revealed that DMT reductively quenches the excited state of [Ru(dpp)3]2+ with a bimolecular rate constant of kq=4.9×109 m−1 s−1. The rate constant measured for electron transfer from the reduced sensitizer to the [Co(dmgH)2pyCl] was found to be near the diffusion limit, kCo=2.4×109 m−1 s−1. H2 production by photocatalysis was independently monitored by using a high‐throughput photochemical reactor equipped with pressure transducers, gas chromatogram, and a mass spectrometer for detection; this illustrated that the composition yields high turnover numbers (TONs), approaching 10 000 (H2/Ru) with respect to the sensitizer and deuteration studies using D2O confirmed that H2 is primarily produced from protons derived from water in these systems.
Broadband matching via reflection function optimization
Authors: Şengül Metin
Published: May 2016

In this paper, a practical approach is presented for designing broadband matching networks via reflection function optimization. In the proposed algorithm, the input or output reflection function of the matching network is expressed in terms of three real polynomials describing the matching network, load and generator reflection coefficients. Next one of the polynomials is optimized to get minimum reflection function values in the passband. Then matching network topology and element values are obtained via the formed input reflection coefficient expression. Two examples are presented to explain the usage of the new approach. Copyright © 2016 John Wiley & Sons, Ltd.
Tumorigenic Properties of Drosophila Epithelial Cells Mutant for lethal giant larvae
Authors: Calleja Manuel , Morata Ginés , Casanova Jordi
Published: May 2016

Background: Mutations in Drosophila tumor suppressor genes (TSGs) lead to the formation of invasive tumors in the brain and imaginal discs. Results: Here we studied the tumorigenic properties of imaginal discs mutant for the TSG gene lethal giant larvae (lgl). lgl mutant cells display the characteristic features of mammalian tumor cells: they can proliferate indefinitely, induce additional tracheogenesis (an insect counterpart of vasculogenesis) and invade neighboring tissues. Lgl mutant tissues exhibit high apoptotic levels, which lead to the activation of the Jun‐N‐Terminal Kinase (JNK) pathway. We propose that JNK is a key factor in the acquisition of these tumorigenic properties; it promotes cell proliferation and induces high levels of Mmp1 and confers tumor cells capacity to invade wild‐type tissue. Noteworthy, lgl RNAi‐mediated down‐regulation does not produce similar transformations in the central nervous system (CNS), thereby indicating a fundamental difference between the cells of developing imaginal discs and those of differentiated organs. We discuss these results in the light of the “single big‐hit origin” of some human pediatric or developmental cancers. Conclusions: Down‐regulation of lgl in imaginal discs is sufficient to enhance tracheogenesis and to promote invasion and colonization of other larval structures including the CNS. Developmental Dynamics 245:834–843, 2016. © 2016 Wiley Periodicals, Inc.
Central‐place foraging and ecological effects of an invasive predator across multiple habitats
Authors: Benkwitt Cassandra E.
Published: May 2016

Cross‐habitat foraging movements of predators can have widespread implications for predator and prey populations, community structure, nutrient transfer, and ecosystem function. Although central‐place foraging models and other aspects of optimal foraging theory focus on individual predator behavior, they also provide useful frameworks for understanding the effects of predators on prey populations across multiple habitats. However, few studies have examined both the foraging behavior and ecological effects of nonnative predators across multiple habitats, and none has tested whether nonnative predators deplete prey in a manner predicted by these foraging models. I conducted behavioral observations of invasive lionfish (Pterois volitans) to determine whether they exhibit foraging movements similar to other central‐place consumers. Then, I used a manipulative field experiment to test whether their effects on prey populations are consistent with three qualitative predictions from optimal foraging models. Specifically, I predicted that the effects of invasive lionfish on native prey will (1) occur at central sites first and then in surrounding habitats, (2) decrease with increasing distance away from their shelter site, and (3) extend to greater distances when prey patches are spaced closer together. Approximately 40% of lionfish exhibited short‐term crepuscular foraging movements into surrounding habitats from the coral patch reefs where they shelter during daylight hours. Over the course of 7 weeks, lionfish depleted native fish populations on the coral patch reefs where they reside, and subsequently on small structures in the surrounding habitat. However, their effects did not decrease with increasing distance from the central shelter site and the influence of patch spacing was opposite the prediction. Instead, lionfish always had the greatest effects in areas with the highest prey densities. The differences between the predicted and observed effects of lionfish foraging are likely due to different constraints faced by invasive predators compared to native predators, namely that lionfish do not face increased predation risk with increased movement away from shelter sites. By foraging at greater distances from patch reefs than native predators, lionfish eliminated a spatial refuge from predation used by juveniles of many commercially and ecologically important reef fishes.
Do the rich get richer? Varying effects of tree species identity and diversity on the richness of understory taxa
Authors: Chamagne Juliette , Paine C. E. Timothy , Schoolmaster Donald R. , Stejskal Robert , Volarřík Daniel , Šebesta Jan , Trnka Filip , Koutecký Tomáš , Švarc Petr , Svátek Martin , Hector Andy , Matula Radim
Published: May 2016

Understory herbs and soil invertebrates play key roles in soil formation and nutrient cycling in forests. Studies suggest that diversity in the canopy and in the understory are positively associated, but these studies often confound the effects of tree species diversity with those of tree species identity and abiotic conditions. We combined extensive field sampling with structural equation modeling to evaluate the simultaneous effects of tree diversity on the species diversity of understory herbs, beetles, and earthworms. The diversity of earthworms and saproxylic beetles was directly and positively associated with tree diversity, presumably because species of both these taxa specialize on certain species of trees. Tree identity also strongly affected diversity in the understory, especially for herbs, likely as a result of interspecific differences in canopy light transmittance or litter decomposition rates. Our results suggest that changes in forest management will disproportionately affect certain understory taxa. For instance, changes in canopy diversity will affect the diversity of earthworms and saproxylic beetles more than changes in tree species composition, whereas the converse would be expected for understory herbs and detritivorous beetles. We conclude that the effects of tree diversity on understory taxa can vary from positive to negative and may affect biogeochemical cycling in temperate forests. Thus, maintaining high diversity in temperate forests can promote the diversity of multiple taxa in the understory.
Could an El Niño event put dietary supplies of n‐3 long‐chain polyunsaturated fatty acids (EPA and DHA) in jeopardy
Authors: Pike Ian H. , Tocher Douglas R.
Published: May 2016

The beneficial effects of n‐3 long‐chain polyunsaturated fatty acids, especially EPA and DHA, for human health are widely recognised. Intakes of these fatty acids in many parts of Europe fall far short of the recommended intake, especially in young people. The most robust evidence from human health studies demonstrating beneficial effects is that for cardiovascular disease. Other beneficial effects have been reported for inflammatory diseases such as rheumatoid arthritis, Crohn's disease and ulcerative colitis, cognitive and visual development in pre‐term infants and on various psychological/behavioural and psychiatric disorders. For European consumers fish is the main source of EPA and DHA, especially oily fish, and in particular farmed Atlantic salmon. With evidence of a strong El Niño type event occurring in the Pacific currently (2015/16), fish stock biomasses have drastically declined and permitted fishing heavily reduced. Subsequent fish oil shortages have resulted in increased substitution of fish oil with vegetable oil in feeds for farmed salmon. A significant fall in EPA and DHA in these fish and a reduction in intake by consumers are expected in the short term. Avoiding fish oil shortages causing reductions in EPA and DHA intake by consumers in the future may be possible through the production of DHA‐rich algal biomass if the cost can be reduced. Genetically modified crops which might also be a source of these fatty acids are unlikely to be acceptable for salmon feeds in Europe in the near future.

Practical applications: If farmed Atlantic salmon is to continue to be an important source of EPA and DHA in European diets, especially those in the UK, consideration will have to be given to obtaining new sources of these fatty acids. It would be prudent to follow the development of cheaper forms of DHA‐rich algal biomass for incorporation into salmon feeds. Any relaxation of the public's objections to the use of genetically modified crops to produce ingredients for salmon feeds should be followed. It may present the opportunity to use, for example, genetically modified Camelina sativa as an alternative source.

For European consumers fish, and especially farmed salmon, are the almost exclusive source of dietary EPA and DHA that are important in the maintenance of health. Salmon obtain most of these fatty acids from fish oil, which in turn is produced mainly in South American waters. With a strong El Niño, a natural periodic warming event, in the Pacific Ocean in 2014/15 fish oil supplies are currently scarce with reduced stocks for salmon feeds. This in turn has reduced availability of EPA and DHA and so alternative sources are suggested.
Cyclic α,α‐Disubstituted α‐Amino Acids with Menthone in Their Side‐Chains Linked through an Acetal Moiety and Helical Structures of Their Peptides
Authors: Furukawa Kaori , Oba Makoto , Opiyo George Ouma , Doi Mitsunobu , Tanaka Masakazu
Published: May 2016

The chiral cyclic α,α‐disubstituted α‐amino acids, Hms[(–)‐Men] and Hms[(+)‐Men] with (–)‐ and (+)‐menthones in their side‐chains, respectively, were designed and synthesized. Hms[(–)‐Men] homopeptides and Hms[(–)/(+)‐Men]‐containing l‐Leu‐based peptides were prepared in order to investigate the conformational properties of Hms[(–)/(+)‐Men]. The preferred conformations of the Hms[(–)/(+)‐Men]‐containing peptides were determined by FTIR, 1H NMR, and CD spectroscopy in solution, and by X‐ray crystallographic analysis in the crystal state. Conformational analysis in solution revealed similar right‐handed (P) 310‐helical structures for the Hms[(–)/(+)‐Men]‐containing octapeptides. In the solid state of the hexapeptides, the peptide main‐chain structures were mostly similar; however, some differences were observed in the side‐chains. The Hms[(–)/(+)‐Men] may function as helical inducers, but their side‐chain chiralities had only a negligible effect on their helical‐screw control of l‐Leu‐based peptides.
Iron‐Catalyzed Arene Prenylation
Authors: Villani‐Gale Alexander J. , Eichman Chad C.
Published: May 2016

The syntheses of prenylated arenes and 2,2‐dimethylchromans using a Friedel–Crafts‐type coupling between activated arenes and isoprene is reported. A combination of catalytic amounts of FeCl3 and AgBF4 promotes a regioselective prenylation event followed by a cyclization to form a 2,2‐dimethylchroman structure. The method avoids isoprene polymerization and allows the facile late‐stage derivatization of biologically active motifs.
Protein Structure‐sensitive Analysis by Normal Pulse Voltammetry
Authors: Černocká Hana , Paleček Emil
Published: May 2016

Earlier we showed that constant current chronopotentiometric stripping (CPS) at mercury‐containing electrodes reflects changes in proteins, such as denaturation, single amino acid exchange or protein damage by physical and chemical agents. Here we attempted to compare performance of the galvanostatic CPS with the potentiostatic normal pulse voltammetry (NPV). We have found that repeated 50 ms or longer NPV pulses denature the surface‐attached protein. Using shorter pulses and adapting other NPV settings we have been able to obtain a good resolution of native (folded) and denatured (unfolded) bovine serum albumin. On the other hand, partial denaturation of the surface‐attached native bovine serum albumin during the potential scanning may prevent detection of small conformational changes in the protein.
Isotretinoin Oxidation and Electroanalysis in a Pharmaceutical Drug Using a Boron‐doped Diamond Electrode
Authors: Machini W. B. S. , Enache T. A. , Jorge S. M. A. , Oliveira‐Brett A. M.
Published: May 2016

Isotretinoin redox behaviour, by voltammetry, at the cathodic pre‐treated boron doped diamond electrode by cyclic, differential pulse and square wave voltammetry, and by spectrophotometry in a wide pH range, was investigated. The isotretinoin oxidation was an irreversible, diffusion‐controlled process, occurred in a three‐step cascade mechanism, and the isotretinoin diffusion coefficient D13‐cis‐RA=7.35×10−6 cm2 s−1, was calculated. The UV‐Vis isotretinoin maximum absorption was pH‐dependent. The detection limits LOD=0.53 μM, by differential pulse voltammetry, and LOD=0.38 μM, by UV‐Vis spectroscopy, were obtained. The isotretinoin in the pharmaceutical drug Roacutan®, using differential pulse voltammetry, was determined.
Determining Which Phenotypes Underlie a Pleiotropic Signal
Authors: Majumdar Arunabha , Haldar Tanushree , Witte John S.
Published: May 2016

Discovering pleiotropic loci is important to understand the biological basis of seemingly distinct phenotypes. Most methods for assessing pleiotropy only test for the overall association between genetic variants and multiple phenotypes. To determine which specific traits are pleiotropic, we evaluate via simulation and application three different strategies. The first is model selection techniques based on the inverse regression of genotype on phenotypes. The second is a subset‐based meta analysisASSET[Bhattacharjee et al.,], which provides an optimal subset of nonnull traits. And the third is a modified Benjamini–Hochberg (B‐H) procedure of controlling the expected false discovery rate [Benjamini and Hochberg,] in the framework of phenome‐wide association study. From our simulations we see that an inverse regression‐based approachMultiPhen[O'Reilly et al.,] is more powerful thanASSETfor detecting overall pleiotropic association, except for when all the phenotypes are associated and have genetic effects in the same direction. For determining which specific traits are pleiotropic, the modified B–H procedure performs consistently better than the other two methods. The inverse regression‐based selection methods perform competitively with the modified B–H procedure only when the phenotypes are weakly correlated. The efficiency ofASSETis observed to lie below and in between the efficiency of the other two methods when the traits are weakly and strongly correlated, respectively. In our application to a large GWAS, we find that the modified B–H procedure also performs well, indicating that this may be an optimal approach for determining the traits underlying a pleiotropic signal.
Effects of uncertainty in head tissue conductivity and complexity on EEG forward modeling in neonates
Authors: Azizollahi Hamed , Aarabi Ardalan , Wallois Fabrice
Published: May 2016

In this study, we investigated the impact of uncertainty in head tissue conductivities and inherent geometrical complexities including fontanels in neonates. Based on MR and CT coregistered images, we created a realistic neonatal head model consisting of scalp, skull, fontanels, cerebrospinal fluid (CSF), gray matter (GM), and white matter (WM). Using computer simulations, we investigated the effects of exclusion of CSF and fontanels, discrimination between GM and WM, and uncertainty in conductivity of neonatal head tissues on EEG forward modeling. We found that exclusion of CSF from the head model induced the strongest widespread effect on the EEG forward solution. Discrimination between GM and white matter also induced a strong widespread effect, but which was less intense than that of CSF exclusion. The results also showed that exclusion of the fontanels from the neonatal head model locally affected areas beneath the fontanels, but this effect was much less pronounced than those of exclusion of CSF and GM/WM discrimination. Changes in GM/WM conductivities by 25% with respect to reference values induced considerable effects in EEG forward solution, but this effect was more pronounced for GM conductivity. Similarly, changes in skull conductivity induced effects in the EEG forward modeling in areas covered by the cranial bones. The least intense effect on EEG was caused by changes in conductivity of the fontanels. Our findings clearly emphasize the impact of uncertainty in conductivity and deficiencies in head tissue compartments on modeling research and localization of brain electrical activity in neonates. Hum Brain Mapp 37:3604–3622, 2016. © 2016 Wiley Periodicals, Inc.
Soil water content in southern England derived from a cosmic‐ray soil moisture observing system – COSMOS‐UK
Authors: Evans J. G. , Ward H. C. , Blake J. R. , Hewitt E. J. , Morrison R. , Fry M. , Ball L. A. , Doughty L. C. , Libre J. W. , Hitt O. E. , Rylett D. , Ellis R. J. , Warwick A. C. , Brooks M. , Parkes M. A. , Wright G. M. H. , Singer A. C. , Boorman D. B. , Jenkins A.
Published: May 2016

Cosmic‐ray soil moisture sensors have the advantage of a large measurement footprint (approximately 700 m in diameter) and are able to operate continuously to provide area‐averaged near‐surface (top 10–20 cm) volumetric soil moisture content at the field scale. This paper presents the application of this technique at four sites in southern England over almost 3 years. Results show the soil moisture response to contrasting climatic conditions during 2011–2014 and are the first such field‐scale measurements made in the UK. These four sites are prototype stations for a UK COsmic‐ray Soil Moisture Observing System, and particular consideration is given to sensor operating conditions in the UK. Comparison of these soil water content observations with the Joint UK Land Environment Simulator 10‐cm soil moisture layer shows that these data can be used to test and diagnose model performance and indicate the potential for assimilation of these data into hydro‐meteorological models. The application of these large‐area soil water content measurements to evaluate remotely sensed soil moisture products is also demonstrated. Numerous applications and the future development of a national COsmic‐ray Soil Moisture Observing System network are discussed. Copyright © 2016 John Wiley & Sons, Ltd.
Dietary inflammatory index and prostate cancer survival
Authors: Zucchetto Antonella , Gini Andrea , Shivappa Nitin , Hébert James R. , Stocco Carmen , Dal Maso Luigino , Birri Silvia , Serraino Diego , Polesel Jerry
Published: May 2016

Systemic inflammatory status has been reported to impact survival of prostate cancer (PCa) patients; however, evidence is lacking on whether the inflammatory potential of diet can influence prognosis of PCa patients. To investigate the association between a dietary inflammatory index (DII) and PCa survival, we conducted a retrospective cohort study including 726 men with PCa originally enrolled, between 1995 and 2002, in an Italian case–control study. Information on diet and Gleason score was collected at PCa diagnosis. DII was derived from a food frequency questionnaire using a validated algorithm. Adjusted hazard ratios (HRs) of death with 95% confidence intervals (CIs) were estimated using a Fine‐Gray model. DII scores were not significantly associated with all‐cause mortality of PCa patients (HR highest vs. lowest DII tertile = 1.25; 95% CI: 0.86–1.83). However, considerable heterogeneity emerged according to Gleason score (p < 0.01): no associations emerged among men with Gleason score 2–6 PCa; whereas, among patients with Gleason score 7–10 PCa, DII was directly associated with both all‐cause and PCa‐specific mortality (HR highestvs. lowest DII tertile: 2.78; 95% CI: 1.41–5.48; and 4.01; 95% CI: 1.25–12.86; respectively). Among patients with Gleason score 7–10 PCa, ten‐year all‐cause survival probabilities were 58% (95% CI: 47–67%) for highest and 78% (95% CI: 67–86%) for lowest DII tertile. Study findings support the hypothesis that diet, through its inflammatory potential, may influence the prognosis of patients with more aggressive PCa. Dietary interventions aimed at decreasing inflammation may be considered to improve survival of men with PCa.
New method for the fabrication of highly osteoconductive β‐1,3‐glucan/HA scaffold for bone tissue engineering: Structural, mechanical, and biological characterization
Authors: Klimek Katarzyna , Przekora Agata , Pałka Krzysztof , Ginalska Grażyna
Published: May 2016

Recent studies have shown that thermal method for β‐1,3‐glucan (curdlan) gelation performed at temperature above 80°C enables fabrication of biocompatible bone scaffolds. The aim of this study was to establish new method for fabrication of β‐1,3‐glucan/hydroxyapatite (glu/HA) scaffold using ion‐exchanging dialysis for curdlan gelation that allows for the modifications of the glu/HA material with thermo‐sensitive agents like growth factors or adhesive proteins. Obtained results reveal that fabricated scaffold appears to be highly osteoconductive as it is nontoxic, promotes osteoblast growth and proliferation as well as increases bone alkaline phosphatase level thereby enhancing cell differentiation. It was demonstrated that developed new method for the glu/HA scaffold fabrication allows to obtain material that not only can be modified with thermo‐sensitive agents at the stage of production process but also is a promising candidate for bone tissue engineering applications to act as a framework for osteoblasts to spread and form new bone. It should be noted that dialysis method for curdlan gelation has never been used before to fabricate bone scaffold. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 2528–2536, 2016.
Modeling and optimization of antibacterial activity of the chitosan‐based hydrogel films using central composite design
Authors: Lahooti Behnaz , Khorram Mohammad , Karimi Gholamreza , Mohammadi Aliakbar , Emami Amir
Published: May 2016

In the present study, hydrogel films composed of chitosan–poly(vinyl alcohol)–gelatin–thyme honey were successfully prepared by casting method, and their anti‐bacterial properties were modeled and optimized. Antibacterial properties of the prepared films were analyzed by applying agar diffusion method. Staphylococcus aureus and Pseudomonas aeruginosa were tested as Gram‐positive and Gram‐negative bacteria, respectively. In order to obtain the composition of the film with maximum inhibition zone against both above‐mentioned bacterial strains, the experiments were designed using response surface methodology based on five‐level central composite design with four parameters, including concentrations of chitosan, poly(vinyl alcohol), gelatin, and honey. The results indicated that the prepared samples had good antibacterial activities against these two studied bacteria strains. Response surface method is conducted to develop mathematical models for process responses. Variance analysis on the experimental data shows that inhibition zone can be predicted effectively with quadratic models. In addition, swelling properties and rate of water vapor transmission of the prepared hydrogel films were studied. Due to the successful results, this hydrogel film has an excellent potential to be explored further as a wound healing material. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 2544–2553, 2016.
Chemical potential and reaction electronic flux in symmetry controlled reactions
Authors: Vogt‐Geisse Stefan , Toro‐Labbé Alejandro
Published: May 2016

In symmetry controlled reactions, orbital degeneracies among orbitals of different symmetries can occur along a reaction coordinate. In such case Koopmans' theorem and the finite difference approximation provide a chemical potential profile with nondifferentiable points. This results in an ill‐defined reaction electronic flux (REF) profile, since it is defined as the derivative of the chemical potential with respect to the reaction coordinate. To overcome this deficiency, we propose a new way for the calculation of the chemical potential based on a many orbital approach, suitable for reactions in which symmetry is preserved. This new approach gives rise to a new descriptor: symmetry adapted chemical potential (SA‐CP), which is the chemical potential corresponding to a given irreducible representation of a symmetry group. A corresponding symmetry adapted reaction electronic flux (SA‐REF) is also obtained. Using this approach smooth chemical potential profiles and well defined REFs are achieved. An application of SA‐CP and SA‐REF is presented by studying the Cs enol‐keto tautomerization of thioformic acid. Two SA‐REFs are obtained,
(ξ) and
(ξ). It is found that the tautomerization proceeds via an in‐plane delocalized 3‐center 4‐electron O‐H‐S hypervalent bond which is predicted to exist only in the transition state (TS) region. © 2016 Wiley Periodicals, Inc.
Segmentation and additive approach: A reliable technique to study noncovalent interactions of large molecules at the surface of single‐wall carbon nanotubes
Authors: Torres Ana M. , Scheiner Steve , Roy Ajit K. , Garay‐Tapia Andrés M. , Bustamante John , Kar Tapas
Published: May 2016

This investigation explores a new protocol, named Segmentation and Additive approach (SAA), to study exohedral noncovalent functionalization of single‐walled carbon nanotubes with large molecules, such as polymers and biomolecules, by segmenting the entire system into smaller units to reduce computational cost. A key criterion of the segmentation process is the preservation of the molecular structure responsible for stabilization of the entire system in smaller segments. Noncovalent interaction of linoleic acid (LA, C18H32O2), a fatty acid, at the surface of a (10,0) zigzag nanotube is considered for test purposes. Three smaller segmented models have been created from the full (10,0)‐LA system and interaction energies were calculated for these models and compared with the full system at different levels of theory, namely ωB97XD, LDA. The success of this SAA is confirmed as the sum of the interaction energies is in very good agreement with the total interaction energy. Besides reducing computational cost, another merit of SAA is an estimation of the contributions from different sections of the large system to the total interaction energy which can be studied in‐depth using a higher level of theory to estimate several properties of each segment. On the negative side, bulk properties, such as HOMO‐LUMO (highest occupied molecular orbital ‐ lowest occupied molecular orbital) gap, of the entire system cannot be estimated by adding results from segment models. © 2016 Wiley Periodicals, Inc.
The Prognostic Significance of Neutrophil‐to‐Lymphocyte and Platelet‐to‐Lymphocyte Ratios in Patients With Multiple Myeloma
Authors: Wongrakpanich Supakanya , George Gemlyn , Chaiwatcharayut Wikrom , Biso Sylvia , Candelario Nellowe , Mittal Varun , Pomerantz Sherry , Varadi Gabor
Published: May 2016

Object

Neutrophil‐to‐lymphocyte ratio (NLR) and platelet‐to‐lymphocyte ratio (PLR) are simple, inexpensive prognostic markers for various conditions. The objective of this study was to determine the prognostic significance of NLR and PLR in patients with multiple myeloma (MM) in terms of survival.

Method

A retrospective chart review study was conducted for 175 patients who met the criterion of diagnosis for MM between January 2004 and September 2014.

Result

The median age of diagnosis was 69 years. Patients were divided into high and low NLR and PLR groups according to cutoff points from the receiver operating characteristic curve (2.78 and 155.58, respectively). The high NLR and PLR groups were associated with lower albumin level and higher staging. The high NLR group experienced inferior median survival compared with the low NLR group (37 vs. 66 months; log‐rank P‐value 0.005). However, there was no significant difference in median survival between the high and low PLR groups (45 vs. 62 months; P = 0.077). Multivariate analysis demonstrated that NLR is an independent predictor for OS of MM (HR 2.892; P = 0.009).

Conclusion

We conclude that NLR is an independent prognostic factor for OS in MM.