bluuebunny/crossref_metadata_2025 huggingface dataset:
Changes in insulin sensitivity and secretion after sleeve gastrectomy
Authors: Casella G , Soricelli E , Castagneto-Gissey L , Redler A , Basso N , Mingrone G
Published: November 2015

Background

Sleeve gastrectomy is indicated for the treatment of obesity and related co-morbidity including diabetes. The dynamic changes in insulin secretion and sensitivity after sleeve gastrectomy are unknown.

Methods

Whole-body insulin sensitivity was measured by the euglycaemic hyperinsulinaemic clamp technique, and insulin secretion by C-peptide deconvolution after an oral glucose tolerance test (OGTT), before and 3, 6 and 12 months after sleeve gastrectomy in morbidly obese subjects. The time course of glucagon-like peptide (GLP) 1, as a marker of insulin secretion following OGTT, was also assessed.

Results

Ten patients were included in the study. Median (range) baseline insulin sensitivity (M-value) increased from 84·0 (20·2–131·4) mmol per kg per min at baseline to 122·8 (99·0–179·3) mmol per kg per min at 12 months after surgery (P = 0·015). Fasting insulin sensitivity, measured by homeostatic model assessment of insulin resistance, which represents a surrogate index of hepatic insulin resistance, decreased from 3·3 (1·9–5·5) to 0·7 (0·5–1·1) mg/dl·µunits/ml (P < 0·001). Total insulin secretion, measured as incremental area under the curve (AUC), after OGTT decreased from 360·4 (347·9–548·0) to 190·1 (10·1–252·0) mmol/l·180 min at 12 months (P = 0·011). The AUC for GLP-1 increased from 258·5 (97·5–552·6) to 5531·8 (4143·0–7540·9) pmol/l·180 min at 12 months after sleeve gastrectomy (P < 0·001). In multiple regression analysis, 51 per cent of the M-value variability was explained by GLP-1 secretion.

Conclusion

Sleeve gastrectomy improved insulin sensitivity and reduced insulin secretion within 6 months after surgery. Although there was a correlation between insulin sensitivity and bodyweight, the major driver of the improvement in insulin sensitivity was GLP-1 secretion.
New Fluorescence Domain “Excited Multimer” Formed upon Photoexcitation of Continuously Stacked Diaroylmethanatoboron Difluoride Molecules with Fused π‐Orbitals in Crystals
Authors: Sakai Atsushi , Ohta Eisuke , Yoshimoto Yuichi , Tanaka Mirai , Matsui Yasunori , Mizuno Kazuhiko , Ikeda Hiroshi
Published: November 2015

The crystal‐packing structures of seven derivatives of diaroylmethanatoboron difluoride (1 a–gBF2) are characterized by no overlap of the π‐conjugated main units of two adjacent molecules (type I), overlap of the benzene ring π‐orbitals of two adjacent molecules (type II), and overlap of the benzene and dihydrodioxaborinine rings π‐orbitals of adjacent molecules (type III). The crystal‐packing structures govern the fluorescence (FL) properties in the crystalline states. The FL domain that is present in type I crystals, in which intermolecular orbital interactions are absent, leads to excited monomer‐like FL properties. In the case of the type II crystals, the presence of intermolecular overlap of the benzene rings π‐orbitals generates new FL domains, referred to as “excited multimers”, which possess allowed S0–S1 electronic transitions and, as a result, similar FL lifetimes at longer wavelengths than the FL of the type I crystals. Finally, intermolecular overlap of the benzene and dihydrodioxaborinine ring π‐orbitals in the type III crystals leads to “excited multimer” domains with forbidden S0–S1 electronic transitions and longer FL lifetimes at similar wavelengths as that in type I crystals.
On the Triple Role of Fluoride Ions in Palladium‐Catalyzed Stille Reactions
Authors: Hervé Marius , Lefèvre Guillaume , Mitchell Emily A. , Maes Bert U. W. , Jutand Anny
Published: November 2015

The mechanism of Stille reactions (cross‐coupling of ArX with Ar′SnnBu3) performed in the presence of fluoride ions is established. A triple role for fluoride ions is identified from kinetic data on the rate of the reactions of trans‐[ArPdBr(PPh3)2] (Ar=Ph, p‐(CN)C6H4) with Ar′SnBu3 (Ar′=2‐thiophenyl) in the presence of fluoride ions. Fluoride ions promote the rate‐determining transmetallation by formation of trans‐[ArPdF(PPh3)2], which reacts with Ar′SnBu3 (Ar′=Ph, 2‐thiophenyl) at room temperature, in contrast to trans‐[ArPdBr(PPh3)2], which is unreactive. However, the concentration ratio [F−]/[Ar′SnBu3] must not be too high, because of the formation of unreactive anionic stannate [Ar′Sn(F)Bu3]−. This rationalises the two kinetically antagonistic roles exerted by the fluoride ions that are observed experimentally, and is found to be in agreement with the kinetic law. In addition, fluoride ions promote reductive elimination from trans‐[ArPdAr′(PPh3)2] generated in the transmetallation step.
A Metal–Organic Framework/DNA Hybrid System as a Novel Fluorescent Biosensor for Mercury(II) Ion Detection
Authors: Wu Lan‐Lan , Wang Zhuo , Zhao Shu‐Na , Meng Xing , Song Xue‐Zhi , Feng Jing , Song Shu‐Yan , Zhang Hong‐Jie
Published: November 2015

Mercury(II) ions have emerged as a widespread environmental hazard in recent decades. Despite different kinds of detection methods reported to sense Hg2+, it still remains a challenging task to develop new sensing molecules to replenish the fluorescence‐based apparatus for Hg2+ detection. This communication demonstrates a novel fluorescent sensor using UiO‐66‐NH2 and a T‐rich FAM‐labeled ssDNA as a hybrid system to detect Hg2+ sensitively and selectively. To the best of our knowledge, it has rarely been reported that a MOF is utilized as the biosensing platform for Hg2+ assay.
A Serendipitous Rendezvous with a Four‐Center Two‐Electron Bonded Intermediate in the Aerial Oxidation of Hydrazine
Authors: Banerjee Ambar , Ganguly Gaurab , Roy Lisa , Pathak Shubhrodeep , Paul Ankan
Published: November 2015

Oxidation by dioxygen has a rich repertoire of mechanistic intricacies. Herein, we report a hitherto unknown paradigm of dioxygen activation reaction which propagates through a four center two electron (4c–2e) bound species. Using static DFT and ab initio quantum chemical techniques we have unraveled the oxidation pathway for hydrazine and its methylated analogues by dioxygen which involves formation of this unconventional 4c–2e bonded species en route to the oxidation products. Inconvertible evidence in favor of such an unprecedented dioxygen activation route is provided by capturing the events of formation of the 4c–2e species in aqueous phase for hydrazine and its congeners and the experimentally observed products from the respective 4c–2e species, like H2O2 and N2H2, diazene in the case of hydrazine using Car–Parrinello molecular dynamics simulations.
Me2Zn‐Mediated Catalytic Enantio‐ and Diastereoselective Addition of TosMIC to Ketones
Authors: Keeri Abdul Raheem , Gualandi Andrea , Mazzanti Andrea , Lewinski Janusz , Cozzi Pier Giorgio
Published: November 2015

The first catalytic asymmetric addition of TosMIC to unactivated ketones is presented. A combination of Me2Zn and aminoalcohol catalyst promoted the aldol addition/cyclization reaction to render oxazolines possessing a fully substituted stereocenter with excellent yields (up to 92 %), high enantioselectivities (up to 96 %), and complete diastereoselectivity. The chiral oxazolines were then used to give, after a straightforward acid hydrolysis, enantioenriched building blocks bearing tertiary alcohol motifs such as hydroxylaldehydes, hydroxylacids, and hydroxylesters without racemization.
Aminobenzimidazoles and Structural Isomers as Templates for Dual‐Acting Butyrylcholinesterase Inhibitors and hCB2R Ligands To Combat Neurodegenerative Disorders
Authors: Dolles Dominik , Nimczick Martin , Scheiner Matthias , Ramler Jacqueline , Stadtmüller Patricia , Sawatzky Edgar , Drakopoulos Antonios , Sotriffer Christoph , Wittmann Hans‐Joachim , Strasser Andrea , Decker Michael
Published: November 2015

A pharmacophore model for butyrylcholinesterase (BChE) inhibitors was applied to a human cannabinoid subtype 2 receptor (hCB2R) agonist and verified it as a first‐generation lead for respective dual‐acting compounds. The design, synthesis, and pharmacological evaluation of various derivatives led to the identification of aminobenzimidazoles as second‐generation leads with micro‐ or sub‐micromolar activities at both targets and excellent selectivity over hCB1 and AChE, respectively. Computational studies of the first‐ and second‐generation lead structures by applying molecular dynamics (MD) on the active hCB2R model, along with docking and MD on hBChE, has enabled an explanation of their binding profiles at the protein levels and opened the way for further optimization. Dual‐acting compounds with “balanced” affinities and excellent selectivities could be obtained that represent leads for treatment of both cognitive and pathophysiological impairment occurring in neurodegenerative disorders.
How to escape from haller's rule: Olfactory system complexity in small and large Trichogramma evanescens parasitic wasps
Authors: van der Woude Emma , Smid Hans M.
Published: November 2015

While Haller's rule states that small animals have relatively larger brains, minute Trichogramma evanescens Westwood (Hymenoptera: Trichogrammatidae) parasitic wasps scale brain size linearly with body size. This linear brain scaling allows them to decrease brain size beyond the predictions of Haller's rule, and is facilitated by phenotypic plasticity in brain size. In the present study we addressed whether this plasticity resulted in adaptations to the complexity of the morphology of the olfactory system of small and large T. evanescens. We used confocal laser scanning microscopy to compare size and number of glomeruli in the antennal lobe in the brain, and scanning electron microscopy to compare length and number of olfactory sensilla on the antennae. The results show a similar level of complexity of the olfactory system morphology of small and large wasps. Wasps with a similar genotype but very different brain and body size have similarly sized olfactory sensilla and most of them occur in equal numbers on the antennae. Small and large wasps also have a similar number of glomeruli in the antennal lobe. Glomeruli in small brains are, however, smaller in both absolute and relative volume. These similarities between small and large wasps may indicate that plasticity in brain size does not require plasticity in the gross morphology of the olfactory system. It may be vital for wasps of all sizes to have a large number of olfactory receptor types, to maintain olfactory precision in their search for suitable hosts, and consequently maintain their reproductive success and Darwinian fitness. J. Comp. Neurol. 524:1876–1891, 2016. © 2015 Wiley Periodicals, Inc.
Generalized Synthesis of Hierarchical Transition Metal Dichalcogenide Nanosheets from Polyoxometalates
Authors: He Peilei , Li Haoyi , Liu Huiling , Wang Xun
Published: November 2015

Transition metal dichalcogenides (TMDs, such as MoS2, WS2 and MoSe2) with lamellar structures have attracted tremendous attention owing to their similar structure to graphite. However, two‐dimensional (2D) TMD nanomaterials display a strong tendency to restack and condense, which leads to a marked decrease of performance in their applications. In this study, we report the synthesis of TMDs by using polyoxometalates (POMs) as tungsten or molybdenum precursors. Hierarchical TMDs with novel structures can be formed below 200 °C, including WS2 rods, MoS2 rods and MoSe2 hollow spheres. All of these structures assembled from the corresponding nanosheets. Meanwhile the epitaxial growth of noble metal nanoparticles (NPs) on TMDs could be achieved very easily. The obtained Pt/WS2 and Pt/MoS2 hybrids were highly active and durable HER catalysts. In addition, the Pt NPs on the surface of TMDs could improve the HER activity sharply, which was likely due to the synergistic effect between Pt NPs and MoS2 rods.
Synthetic Developments of Nontoxic Quantum Dots
Authors: Das Adita , Snee Preston T.
Published: November 2015

Semiconductor nanocrystals, or quantum dots (QDs), are candidates for biological sensing, photovoltaics, and catalysis due to their unique photophysical properties. The most studied QDs are composed of heavy metals like cadmium and lead. However, this engenders concerns over heavy metal toxicity. To address this issue, numerous studies have explored the development of nontoxic (or more accurately less toxic) quantum dots. In this Review, we select three major classes of nontoxic quantum dots composed of carbon, silicon and Group I–III–VI elements and discuss the myriad of synthetic strategies and surface modification methods to synthesize quantum dots composed of these material systems.
Effect of Molecular Coupling on Ultrafast Electron‐Transfer and Charge‐Recombination Dynamics in a Wide‐Gap ZnS Nanoaggregate Sensitized by Triphenyl Methane Dyes
Authors: Debnath Tushar , Maity Partha , Dana Jayanta , Ghosh Hirendra N.
Published: November 2015

Wide‐band‐gap ZnS nanocrystals (NCs) were synthesized, and after sensitizing the NCs with series of triphenyl methane (TPM) dyes, ultrafast charge‐transfer dynamics was demonstrated. HRTEM images of ZnS NCs show the formation of aggregate crystals with a flower‐like structure. Exciton absorption and lumimescence, due to quantum confinement of the ZnS NCs, appear at approximately 310 and 340 nm, respectively. Interestingly, all the TPM dyes (pyrogallol red, bromopyrogallol red, and aurin tricarboxylic acid) form charge‐transfer complexes with the ZnS NCs, with the appearance of a red‐shifted band. Electron injection from the photoexcited TPM dyes into the conduction band of the ZnS NCs is shown to be a thermodynamically viable process, as confirmed by steady‐state and time‐resolved emission studies. To unravel charge‐transfer (both electron injection and charge recombination) dynamics and the effect of molecular coupling, femtosecond transient absorption studies were carried out in TPM‐sensitized ZnS NCs. The electron‐injection dynamics is pulse‐width‐limited in all the ZnS/TPM dye systems, however, the back electron transfer differs, depending on the molecular coupling of the sensitizers (TPM dyes). The detailed mechanisms for the above‐mentioned processes are discussed.
Cu‐Based Nanocomposites as Multifunctional Catalysts
Authors: Kumar Bharat , Rao Gyandshwar Kumar , Saha Soumen , Ganguli Ashok K.
Published: November 2015

Herein, we report the synthesis of Cu/Cu2O nanocomposites by a one‐step hydrothermal process at 180 °C, for which the resulting morphology is dependent on the hydrothermal reaction time (24, 72, and 120 h). With a longer reaction time of 120 h, a rod‐shape morphology is obtained, whereas at 72 and 24 h assemblies of nanoparticles are obtained. The rod‐shaped (120 h) particles of the Cu/Cu2O nanocomposites show a much higher efficiency (6.3 times) than the agglomerates and 2.5 times more than the assemblies of nanoparticles for the hydrogen‐evolution reaction. During the oxygen‐evolution reaction, the nanorods produce a current that is 5.2 and 3.7 times higher than that produced by the agglomerated and assembled nanoparticles, respectively. The electrocatalysts are shown to be highly stable for over 50 cycles. As catalysts for organic synthesis, a 100 % yield is achieved in the Sonogashira cross‐coupling reaction with the nanorods, which is higher than with the other nanocomposite particles. This result demonstrates the significant enhancement of yield obtained with the nanorods for cross‐coupling reactions.
Scalable Preparation of Ternary Hierarchical Silicon Oxide–Nickel–Graphite Composites for Lithium‐Ion Batteries
Authors: Wang Jing , Bao Wurigumula , Ma Lu , Tan Guoqiang , Su Yuefeng , Chen Shi , Wu Feng , Lu Jun , Amine Khalil
Published: November 2015

Silicon monoxide is a promising anode candidate because of its high theoretical capacity and good cycle performance. To solve the problems associated with this material, including large volume changes during charge‐discharge processes, we report a ternary hierarchical silicon oxide–nickel–graphite composite prepared by a facile two‐step ball‐milling method. The composite consists of nano‐Si dispersed silicon oxides embedded in nano‐Ni/graphite matrices (Si@SiOx/Ni/graphite). In the composite, crystalline nano‐Si particles are generated by the mechanochemical reduction of SiO by ball milling with Ni. These nano‐Si dispersed oxides have abundant electrochemical activity and can provide high Li‐ion storage capacity. Furthermore, the milled nano‐Ni/graphite matrices stick well to active materials and interconnect to form a crosslinked framework, which functions as an electrical highway and a mechanical backbone so that all silicon oxide particles become electrochemically active. Owing to these advanced structural and electrochemical characteristics, the composite enhances the utilization efficiency of SiO, accommodates its large volume expansion upon cycling, and has good ionic and electronic conductivity. The composite electrodes thus exhibit substantial improvements in electrochemical performance. This ternary hierarchical Si@SiOx/Ni/graphite composite is a promising candidate anode material for high‐energy lithium‐ion batteries. Additionally, the mechanochemical ball‐milling method is low cost and easy to reproduce, indicating potential for the commercial production of the composite materials.
Catalytic Upgrading of 5‐Hydroxymethylfurfural to Drop‐in Biofuels by Solid Base and Bifunctional Metal–Acid Catalysts
Authors: Bohre Ashish , Saha Basudeb , Abu‐Omar Mahdi M.
Published: November 2015

Design and synthesis of effective heterogeneous catalysts for the conversion of biomass intermediates into long chain hydrocarbon precursors and their subsequent deoxygenation to hydrocarbons is a viable strategy for upgrading lignocellulose into distillate range drop‐in biofuels. Herein, we report a two‐step process for upgrading 5‐hydroxymethylfurfural (HMF) to C9 and C11 fuels with high yield and selectivity. The first step involves aldol condensation of HMF and acetone with a water tolerant solid base catalyst, zirconium carbonate (Zr(CO3)x), which gave 92 % C9–aldol product with high selectivity at nearly 100 % HMF conversion. The as‐synthesised Zr(CO3)x was analysed by several analytical methods for elucidating its structural properties. Recyclability studies of Zr(CO3)x revealed a negligible loss of its activity after five consecutive cycles over 120 h of operation. Isolated aldol product from the first step was hydrodeoxygenated with a bifunctional Pd/Zeolite‐β catalyst in ethanol, which showed quantitative conversion of the aldol product to n‐nonane and 1‐ethoxynonane with 40 and 56 % selectivity, respectively. 1‐Ethoxynonane, a low oxygenate diesel range fuel, which we report for the first time in this paper, is believed to form through etherification of the hydroxymethyl group of the aldol product with ethanol followed by opening of the furan ring and hydrodeoxygenation of the ether intermediate.
High‐performance Polymer Membranes with Multi‐functional Amphiphilic Micelles for CO2 Capture
Authors: Kim Sang Jin , Jeon Harim , Kim Dong Jun , Kim Jong Hak
Published: November 2015

Invited for this month′s cover is the group of Jong Hak Kim at Yonsei University in South Korea. The image shows how CO2 selectively permeates through the polymer membrane containing multi‐functional amphiphilic poly(dimethylsiloxane)‐g‐poly(oxyethylene methacrylate) (PDMS‐g‐POEM) comb copolymer micelles. The microphase‐separated structure consists of PDMS cores and CO2‐philic POEM corona. The Full Paper itself is available at 10.1002/cssc.201501063.
Photo‐oxidation of Polymers Synthesized by Plasma and Initiated CVD
Authors: Baxamusa Salmaan H. , Suresh Aravind , Ehrmann Paul , Laurence Ted , Hanania Jiries , Hayes Jeff , Harley Stephen , Burkey Daniel D.
Published: November 2015

Plasma polymers are often limited by their susceptibility to spontaneous and photo‐oxidation. We show that the unusual photoluminescence (PL) behavior of a plasma polymer of trans‐2‐butene is correlated with its PL strength. These photo‐processes occur under blue light illumination (λ = 405 nm), distinguishing them from traditional ultraviolet degradation of polymers. These photo‐active defects are likely formed during the plasma deposition process, and we show that a polymer synthesized using initiated (i)CVD, a non‐plasma method, has 1000× lower PL signal and enhanced photo‐stability. Non‐plasma methods, such as iCVD, may therefore be a route to overcoming material aging issues that limit the adoption of plasma polymers.
Current state of knowledge on Takotsubo syndrome: a Position Statement from the Taskforce on Takotsubo Syndrome of the Heart Failure Association of the European Society of Cardiology
Authors: Lyon Alexander R. , Bossone Eduardo , Schneider Birke , Sechtem Udo , Citro Rodolfo , Underwood S. Richard , Sheppard Mary N. , Figtree Gemma A. , Parodi Guido , Akashi Yoshihiro J. , Ruschitzka Frank , Filippatos Gerasimos , Mebazaa Alexandre , Omerovic Elmir
Published: November 2015

Takotsubo syndrome is an acute reversible heart failure syndrome that is increasingly recognized in modern cardiology practice. This Position Statement from the European Society of Cardiology Heart Failure Association provides a comprehensive review of the various clinical and pathophysiological facets of Takotsubo syndrome, including nomenclature, definition, and diagnosis, primary and secondary clinical subtypes, anatomical variants, triggers, epidemiology, pathophysiology, clinical presentation, complications, prognosis, clinical investigations, and treatment approaches. Novel structured approaches to diagnosis, risk stratification, and management are presented, with new algorithms to aid decision‐making by practising clinicians. These also cover more complex areas (e.g. uncertain diagnosis and delayed presentation) and the management of complex cases with ongoing symptoms after recovery, recurrent episodes, or spontaneous presentation. The unmet needs and future directions for research in this syndrome are also discussed.
Cytosolic phospholipase A2α has a crucial role in the pathogenesis of DSS‐induced colitis in mice
Authors: Rosengarten Marina , Hadad Nurit , Solomonov Yulia , Lamprecht Sergio , Levy Rachel
Published: November 2015

Colitis, an inflammation of the colon, is a well‐characterized massive tissue injury. Cytosolic phospholipase A2α (cPLA2α) upregulation plays an important role in the development of several inflammatory diseases. The aim of the present study was to define the role of cPLA2α upregulation in the development of colitis. We used a mouse model of dextran sulfate sodium induced colitis. Immunoblotting analysis showed that cPLA2α and NF‐κB were upregulated and activated in the colon from day 2 of colitis induction. This molecular event preceded the development of the disease, as determined by Disease Activity Index score, body weight, colon length, and the expression of colonic inflammatory markers, including neutrophil infiltration detected by myeloperoxidase and by NIMP‐R14, ICAM‐1, COX‐2, iNOS upregulation and LTB4 and TNF‐α secretion. Prevention of cPLA2α upregulation and activity in the colon by i.v. administration of specific antisense oligonucleotides against cPLA2α 1 day prior and every day of exposure to dextran sulfate sodium significantly impeded the development of the disease and prevented NF‐κB activation, neutrophils infiltration into the colonic mucosa, and expression of proinflammatory proteins in the colon. Our results demonstrate a critical role of cPLA2α upregulation in inflammation and development of murine colitis.
γδ T cells support gut Ag‐reactive colitogenic effector T‐cell generation by enhancing Ag presentation by CD11b+ DCs in the mesenteric LN
Authors: Do Jeongsu , Visperas Anabelle , Freeman Michael L. , Jang Eunjung , Kim Sohee , Malissen Bernard , Min Booki
Published: November 2015

T cells expressing the γδ TCR are dominant T‐cell subsets in the intestinal immune system. We previously demonstrated that γδ T cells play important roles in augmenting Th17‐type colitogenic immune responses in a T‐cell‐induced colitic inflammation model. However, its underlying mechanism remains poorly understood. In this study, an in vitro coculture system using effector T cells enriched in gut Ag‐reactive cells was employed as a readout tool to search for gut Ag presenting APCs. We found that the presence of γδ T cells dramatically enhances gut Ag presentation within the mLN in mice. Gut Ag presentation by CD11b+ DC subsets was particularly controlled by γδ T cells. Interestingly, γδ T‐cell entry to the lymph nodes was essential to improve the Ag presentation. Therefore, our results highlight that γδ T cells play a previously unrecognized role to support colitogenic immunity by regulating gut Ag presentation in the draining LN.
Towards Cardiolite‐Inspired Carbon Monoxide Releasing Molecules – Reactivity of d4, d5 Rhenium and d6 Manganese Carb­onyl Complexes with Isocyanide Ligands
Authors: Kottelat Emmanuel , Chabert Valentin , Crochet Aurélien , Fromm Katharina M. , Zobi Fabio
Published: November 2015

Carbon monoxide releasing molecules (CORMs) are investigated widely in synthetic and medicinal chemistry owing to the potential therapeutic applications of the CO gas. Organometallic carbonyl complexes are best suited to play the role of CO carriers as they allow the exogenous release of CO under controlled conditions, and the toxicity of the gas can be overcome. With the long‐term goal of developing CORMs with similar properties to those of the sesta‐methoxyisobutylisonitrile (sesta‐mibi) 99mTc complex (Cardiolite), we have studied the reactivity of isocyanide ligands towards 16‐ and 17‐electron cis‐[Re(CO)2Br4]–/2– species and the [Mn(CO)5Br] complex. Six different isocyanide ancillary ligands (CNR), including mibi, were selected for this study. Their reactions with cis‐dicarbonyl ReIII and ReII complexes were accompanied by two‐ and one‐electron reduction of the metal center and resulted in the formation of stable cis‐mer‐[Re(CO)2(CNR)3Br] species, whereas the same reactions with [Mn(CO)5Br] gave fac‐[Mn(CO)3(CNR)2Br] compounds. All of the complexes were fully characterized, and single‐crystal X‐ray diffraction structure determinations were performed for selected species. In addition, unique monocarbonyl complexes were obtained from the reactions of cis‐[Re(CO)2Br4]– (1) with tert‐butyl isocyanide and cis‐[Re(CO)2Br4]2– (2) with mibi. The species, a heptacoordinate ReIII and a hexacoordinate ReII complex, respectively, were also characterized structurally. The CO‐releasing profiles, the cytotoxic effects against 3T3 fibroblast cells, and the antibacterial properties of the compounds were also investigated.
Synthesis and Photoluminescence Properties of CuI Complexes with Chelating Phosphinito Phosphinine Ligands
Authors: Chen Xiaodan , Li Zhongshu , Yanan Fan , Grützmacher Hansjörg
Published: November 2015

The reaction between the sodium salt of 2‐oxyphosphinine and diphenylchlorophosphine leads to 2‐diphenylphosphinite phosphinine as a new chelating ligand. Copper(I) complexes are easily and quantitatively obtained when this compound is reacted with CuIX (X = Cl, Br, I). The optical properties of these complexes were investigated; all of them show phosphorescence in the solid state at room temperature and emit orange‐red light in the range 658 to 702 nm with average lifetimes from 19.98 to 25.01 μs. The emission wavelength is tuned by the nature of the halide ligand: Cl–, which leads to a larger ligand‐field splitting, gives the longest emission wavelength, whereas I–, which generates a smaller ligand‐field splitting, leads to the shortest emission wavelength.
Synthesis, Structures and Properties of Half‐Sandwich Nickel(II) Complexes with Backbone‐Modified NHC Ligands
Authors: Banach Łukasz , Guńka Piotr A. , Górska Dominika , Podlewska Maja , Zachara Janusz , Buchowicz Włodzimierz
Published: November 2015

A series of seven nickel complexes [Ni(η5‐C5H5)(X)(NHC)] (X = Cl or Br; NHC = N‐heterocyclic carbene) containing backbone‐modified NHC ligands was prepared by treatment of nickelocene with the corresponding NHC·HX salts or, in the case of complex 1h [Ni(η5‐C5H5)(Cl)(IMesO)] (IMesO = 4‐oxo‐1,3‐bis(2,4,6‐trimethylphenyl)imidazolin‐2‐ylidene), by deprotection of the corresponding NHC ligand in complex 1g [Ni(η5‐C5H5)(Cl)(IMesOPiv)] [IMesOPiv = 4‐(pivaloyloxy)‐1,3‐bis(2,4,6‐trimethylphenyl)imidazol‐2‐ylidene]. Single‐crystal X‐ray structures were determined for complexes 1d [Ni(η5‐C5H5)(Cl)(Bn2‐bimy)] (Bn2‐bimy = 1,3‐dibenzylbenzimidazolin‐2‐ylidene), 1g and 1h. The coordination spheres around the nickel atoms resemble those of d8 NiL4 square‐planar complexes, with Ni–C(Cp) bond length differentiation and C–C bond alternation in Cp ligands being taken into account. Desymmetrization of the five‐membered heterocyclic ring and a tautomeric equilibrium were observed for complex 1h. All new complexes are efficient precatalysts in three C–C bond‐forming reactions (polymerization of styrene, polymerization of methyl methacrylate, Suzuki–Miyaura cross‐coupling).
Diastereoselective Synthesis of the A‐B‐C Tricyclic Ring Structure of Stemocurtisine
Authors: Dau Xuan Duc , Willis Anthony C. , Pyne Stephen G.
Published: November 2015

The diastereoselective synthesis of the A‐B‐C tricyclic ring structure of the Stemona alkaloid stemocurtisine is described. This tricyclic precursor to the natural product was obtained in 19 steps from a known vinyl iodide. Attempts to prepare the C‐3a–C‐11 ether moiety of this alkaloid through a photochemically induced oxidative cyclization method were unsuccessful because of the cleavage of the A‐ring.
Recent Advances in First‐Row‐Transition‐Metal‐Catalyzed Dehydrogenative Cou­pling of C(sp3)–H Bonds
Authors: Miao Jinmin , Ge Haibo
Published: November 2015

Transition‐metal‐catalyzed cross dehydrogenative coupling is a highly efficient tool for functionalization of C(sp3)–H bonds. In particular, the inexpensive first‐row transition metals have been demonstrated as effective catalysts in this process. This microreview summarizes recent progress in two classes of first‐row‐transition‐metal‐catalyzed dehydrogenative reactions: intramolecular cyclization for C–C bond formation, and directed site‐selective C–H functionalization. These transformations provide concise and practical approaches for preparation of various organic compounds, but so far they are underdeveloped.
Feed‐Splitting as Energy‐Saving Technique in the Heterogeneous Distillation of Ethanol–Water Azeotropes
Authors: Tavan Yadollah , Shahhosseini Shahrokh
Published: November 2015

The separation of azeotropic mixtures is one of the most energy‐intensive separations in petrochemical processes. In this study the effect of feed‐splitting on one arrangement with heat integration is investigated in order to reduce the energy demand of the heterogeneous azeotropic distillation of ethanol–water process, using Hysys process simulation software and relevant optimization analysis. The total energy demands of the new and conventional processes are compared, revealing that a 27.5 % reduction in energy is possible for the intensified process.
Lead exposure reduces carotenoid-based coloration and constitutive immunity in wild mallards
Authors: Vallverdú-Coll Núria , Mougeot François , Ortiz-Santaliestra Manuel E. , Rodriguez-Estival Jaime , López-Antia Ana , Mateo Rafael
Published: November 2015

The ingestion of spent lead (Pb) from ammunition is a known cause of mortality in waterfowl, but little is known about sublethal effects produced by Pb poisoning on birds, especially in wild populations. The authors studied potential sublethal effects associated with Pb exposure in mallards (Anas platyrhynchos) from the Ebro delta (northeastern Spain) after a ban on Pb ammunition. They analyzed the relationships between blood Pb levels and oxidative stress, immune response, and carotenoid-based coloration, which are known to be influenced by oxidative stress. Levels of Pb were reduced by half from 6 yr to 9 yr after the ban. Lipid peroxidation was positively related to Pb levels in females. The δ-aminolevulinic acid dehydratase activity was suppressed by Pb exposure and negatively associated with the activity of antioxidant enzymes. Carotenoid levels were positively associated with blood Pb concentration in both sexes, and males with higher Pb levels presented a less intense coloration in legs and beak. Levels of Pb were positively related to hemolytic activity of circulating immune system components and negatively related to lysozyme levels. In summary, Pb exposure was associated in a gender-specific way with increased oxidative stress, consequences on color expression, and impaired constitutive immunity. In females, antioxidants seemed to be allocated mostly in reproduction rather than in self-maintenance, whereas males seemed to better maintain oxidative balance to the detriment of coloration. Environ Toxicol Chem 2016;35:1516–1525. © 2015 SETAC
A low‐complexity turbo MUD for MU–MIMO SC‐FDMA systems
Authors: Chang Yu‐Kuan , Ueng Fang‐Biau , Yang Ying‐Mu
Published: November 2015

In order to provide high‐quality services, current communication systems require high data‐transmission rate and good error performance. Single carrier‐frequency division multiple access (SC‐FDMA) has been adopted as the uplink transmission standard in fourth generation cellular network to enable the power efficiency transmission in mobile station. Multi‐user multiple‐input multiple‐output (MU–MIMO) technologies are adopted in many standards to enhance the data rate and the link robustness. By combining MU–MIMO techniques with the SC‐FDMA modulation scheme, MU–MIMO SC‐FDMA systems can achieve high data rates over broadband wireless channels. For MU–MIMO SC‐FDMA systems, possible detection techniques include zero‐forcing detection, minimum mean squared error detection and maximum likelihood detection (MLD). Among these schemes, MLD is optimal, but its complexity grows exponentially with the number of symbols detected. As a result, there are demands for near MLD schemes that provide similar performance with less complexity. In this paper, we consider the MU–MIMO SC‐FDMA communication and propose a low‐complexity and high‐performance turbo receiver for the systems. Some simulation examples for uplink scenario are given to demonstrate the effectiveness of the proposed scheme. Copyright © 2015 John Wiley & Sons, Ltd.
Applicability of the pre‐death grief concept to dementia family caregivers in Asia
Authors: Liew Tau Ming
Published: November 2015

Objective

Pre‐death grief is prevalent among dementia family caregivers. When unaddressed, it produces adverse outcomes. With its research primarily conducted in Caucasians, its applicability to non‐Caucasians is uncertain. We explore the existence and the characteristics of pre‐death grief in a multi‐ethnic Asian population using an established pre‐death grief scale—Marwit–Meuser Caregiver Grief Inventory (MM‐CGI).

Methods

Seventy‐two dementia family caregivers were recruited from a tertiary hospital. Existence of pre‐death grief was shown by its measurability on MM‐CGI, together with good internal consistency reliability and construct validity. Characteristics of pre‐death grief were explored through multivariate linear regression of MM‐CGI and by comparing MM‐CGI scores with those from the original US study using one‐sample T‐test.

Results

In the Asian context, pre‐death grief was measurable in a reliable and valid manner. Risk factors of pre‐death grief included caring for patients with severe dementia, spousal relationship and secondary or below education. Influence of culture was palpable—Asians had more worries and felt isolation, and certain ethnicity showed more pre‐death grief.

Conclusions

Pre‐death grief is applicable even to the non‐Caucasian population. It bears much similarity to that in Caucasians. Yet, its expression is modified by culture. Clinicians working with non‐Caucasian populations need to be sensitive to its presence and to the influence of culture on its expression. © 2015 The Authors. International Journal of Geriatric Psychiatry published by John Wiley & Sons, Ltd.
Raster‐scanned intensity‐controlled carbon ion therapy for mucosal melanoma of the paranasal sinus
Authors: Mohr Angela , Chaudhri Naved , Hassel Jessica C. , Federspil Philippe A. , Vanoni Valentina , Debus Jürgen , Jensen Alexandra D.
Published: November 2015

Background

The purpose of this study was to evaluate the use of raster‐scanned intensity‐controlled carbon ion therapy (ICCT) in the treatment of mucosal melanoma of the paranasal sinus.

Methods

Patients received combined intensity‐modulated radiotherapy (IMRT) plus carbon ion (C12). Records of 18 consecutive patients treated between 2009 and 2013 were analyzed retrospectively regarding toxicity (Common Terminology Criteria for Adverse Events, version 4), treatment response (Response Evaluation Criteria in Solid Tumors [RECIST]), and control/survival rates.

Results

Most patients had advanced disease (T4, 94%; gross residual disease, 78%). Median dose was 74 GyE (median boost volume = 157 mL). C12 treatments were planned as ICCT, no concurrent chemotherapy was administered. Grade III or higher late toxicity was not observed. Overall survival (OS), progression‐free survival (PFS), and locoregional control at 3 years were 16.2%, 0%, and 58.3%, respectively (median follow‐up, 18 months). Resection status did not impact locoregional control or survival rates.

Conclusion

ICCT results in promising locoregional control at mild toxicity. OS is poor because of the occurrence of distant metastases; therefore, addition of systemic components to primary treatment should be investigated. © 2015 Wiley Periodicals, Head Neck 38: E1445–E1451, 2016
Prospective randomized controlled trial to compare 3‐dimensional conformal radiotherapy to intensity‐modulated radiotherapy in head and neck squamous cell carcinoma: Long‐term results
Authors: Ghosh–Laskar Sarbani , Yathiraj Prahlad H. , Dutta Debnarayana , Rangarajan Venkatesh , Purandare Nilendu , Gupta Tejpal , Budrukkar Ashwini , Murthy Vedang , Kannan Sadhana , Agarwal Jai Prakash
Published: November 2015

Background

Grade ≥2 acute xerostomia between 3D conformal radiotherapy (RT) and intensity‐modulated radiotherapy (IMRT) was evaluated in patients with head and neck squamous cell carcinomas (HNSCCs) treated radically.

Methods

Between 2005 and 2007, 59 patients with HNSCC (T1–3, N0–2b) were randomized to IMRT or 3D‐RT. On RT, weekly xerostomia, dysphagia, dermatitis, and mucositis were graded by Radiation Therapy Oncology Group (RTOG) acute toxicity criteria. Patients underwent examination under anesthesia, positron emission tomography (PET)‐CT, and toxicity assessments per protocol (NCT00652613) thereafter.

Results

Incidence of grade ≥2 xerostomia at 8 weeks posttreatment was significantly lower with IMRT compared with 3D conformal RT (24% vs 53%; p = .024). At subsequent follow‐up, significantly fewer patients receiving IMRT had grade ≥2 xerostomia. Long‐term weight loss was higher in patients in the 3D conformal RT arm compared to IMRT (50% vs 21%; p = .038). Disease‐related outcomes between arms (median follow‐up, 70 months) were similar.

Conclusion

IMRT significantly reduces incidence of acute and late grade ≥2 xerostomia in patients with HNSCC. © 2015 Wiley Periodicals, Inc. Head Neck 38: E1481–E1487, 2016
The Role of Interfaces in Enabling Transformational Systems Engineering
Authors: Sawyer George
Published: November 2015

Years ago, Eberhardt Rechtin and Mark Maier observed that “the greatest leverage in [systems] architecting is at the interfaces,” meaning that interfaces are the key to managing complexity and reusing existing entities in a new or revised system. The extension of this observation is that interfaces are also the greatest leverage in the systems development process itself, thus permitting customization of these processes to the unique aspects of the system‐to‐be. Instead of tailoring down a single monolithic systems development process, it may be more advantageous to constructively define a custom process by connecting the defined interfaces of development practices. Evolving systems development methods such as agile systems engineering and design thinking provides a pallet of practices for augmenting or hybridizing classical systems engineering. However effectively aggregating these practices into a cohesive and effective method presents its own set of challenges. A “plug and play” approach to combining methods is a conceptually attractive approach to the challenge of effectively combining practices. However, past experience shows that engineering plug and play architecture for custom systems development is not a trivial process and requires careful design of the interfaces supporting the interconnecting of parts into a useful whole. To enable “fully digital systems development,” these interfaces must also be well‐defined and realizable by engineering tools — abstract and conceptual process definitions will not support this concept. This paper examines the role of interfaces in leveraging existing or new systems development practices and outlines the activities and challenges associated with this undertaking.
An Architectural Patterns Library to aid Systems of Systems Engineering
Authors: Deiotte Ray
Published: November 2015

Systems of Systems (SoS) are rapidly coming to dominate the engineering landscape. However, there are no structures or formalisms for their design, development, adoption, operation, and management. In other words, nearly every SoS Engineering (SoSE) project is a new work, building from the ground up, relying upon foundations built before, but not shared with the larger community. They remain unshared, not because of a lack of willingness, rather because there is no effective mechanism to share information on SoS without revealing proprietary information or trade secrets. In an effort to advance the science and art of SoSE and provide a mechanism for sharing information without infringing on propriety, we introduce the concept of SoS patterns, a SoS pattern library and propose to share it with the community. Rather than taking a purely theoretical view of SoS patterns (which is necessary), we provide a more pragmatic approach: building patterns from experience, providing helpful tools now while refining the generic, nominal patterns. We find that this approach provides not only an incremental, near‐term benefit, but also provides decision makers the information and evidence to assess risk and make informed decisions. In this paper, we describe a brief history of patterns, discuss their applicability and usefulness to the SoS problem, the components of a pattern and provide an example and vision for an open library of patterns for use by, and contribution from, the SoS community at large.
What Every Systems Engineer Needs to Understand about Business Models
Authors: Amon Lee
Published: November 2015

Practitioners of systems engineering are facing challenges as daunting as any seen in the history of the field. In order to respond to these challenges effectively, and to leverage all the benefits possible from transformational systems engineering techniques, the Transformation Caucus believes that systems engineers must be part of the decision process at the business level. This paper discusses and examines several business models and the impacts of the business model chosen on the effectiveness of transformational systems engineering techniques.
Replicating the Results in ‘A New Model of Trend Inflation’ Using Particle Markov Chain Monte Carlo
Authors: Nonejad Nima
Published: November 2015

An article by Chan et al. () published in the Journal of Business and Economic Statistics introduces a new model for trend inflation. They allow the trend inflation to evolve according to a bounded random walk. In order to draw the latent states from their respective conditional posteriors, they use accept–reject Metropolis–Hastings procedures. We reproduce their results using particle Markov chain Monte Carlo (PMCMC), which approaches drawing the latent states from a different technical point of view by relying on combining Markov chain Monte Carlo and sequential Monte Carlo methods. To conclude: we are able to reproduce the results of Chan et al. (). Copyright © 2015 John Wiley & Sons, Ltd.
Prediction of amino acid positions specific for functional groups in a protein family based on local sequence similarity
Authors: Karasev Dmitry A. , Veselovsky Alexander V. , Oparina Nina Yu. , Filimonov Dmitry A. , Sobolev Boris N.
Published: November 2015

The exchange of single amino acid residue in protein can substantially affect the specificity of molecular recognition. Many protein families can be divided into the groups based on specificity to recognized ligands. Prediction of group‐discriminating residues within the certain family is extremely necessary for theoretical studies, enzyme engineering, drug design, and so on. The most existing methods use the multiple sequence alignment. They have the limitations in prediction accuracy due to the family sequence divergence and ligand‐based grouping. We developed a new method SPrOS (Specificity Projection On Sequence) for estimating the specificity of residues to user‐defined groups. SPrOS compares the sequence segments from the test protein and training proteins. Contrary to other segment‐comparison approaches extracting the string motifs, SPrOS calculates the scores for single positions by the similarity of their surroundings. The method was evaluated on the simulated sequences and real protein families. The high‐prediction accuracy was achieved for simulated sequences, in which SPrOS detected specific positions not predicted with the alignment‐based method. For bacterial transcription factors (LacI/GalR) clearly divided into functional groups, the predicted specific residues corresponded to the published experimental data. In a more complicated case of protein kinases classified by inhibitor specificity, the positions predicted with high significance were located in ligand‐binding areas. As the ligand specificity is not necessary coincided with phylogeny, evolutionary‐coupled mutations could disturb the detection of ligand‐specific residues. Excluding proximate homologs of the test protein kinase from the training set, we improved the prediction of the ligand‐specific residues. The SPrOS is available at http://www.way2drug.com/spros/ Copyright © 2015 John Wiley & Sons, Ltd.
Aqueous size‐exclusion chromatographic separations of intact proteins under native conditions: Effect of pressure on selectivity and efficiency
Authors: De Vos Jelle , Kaal Erwin R. , Swart Remco , Baca Martyna , Heyden Yvan Vander , Eeltink Sebastiaan
Published: November 2015

The selectivity and separation efficiency of aqueous size‐exclusion chromatographic separations of intact proteins were assessed for different flow rates, using columns packed with 3 and 5 μm silica particles containing 150 and 290 Å stagnant pores. A mixture of intact proteins with molecular weights ranging between 17 000 and 670 000 Da was used to construct the calibration curves. Both the model fit and the predictive properties, using a leave‐one‐out strategy, of different polynomial models (up to fifth order) were evaluated for different flow rates. The best compromise between model fit and predictive properties was obtained using a third‐order polynomial model. The accuracy of the predictive properties decreased with 10% with an eightfold increase in the flow rate. No changes in retention factors (hence selectivity) were observed in the flow‐rate range applied. A strong correlation between molecular weight and plate height was observed. Exclusion of large‐molecular‐weight proteins led to a significant reduction in the stationary‐phase mass‐transfer contribution to the total plate‐height value, and this effect was also independent of the flow rate applied. The kinetic‐performance limits, in terms of plate number and time, and optimal column‐length particle‐size combinations were determined at the maximum recommended operating pressure of the size‐exclusion chromatography columns (20 MPa). Finally, the possibilities of method speed‐up using ultra‐high‐pressure size‐exclusion chromatography in combination with columns packed with sub‐2 μm particles are discussed.