bluuebunny/crossref_metadata_2025 huggingface dataset:
Copper(I)‐Catalyzed Highly Regio‐ and Stereoselective Hydrosilylation of Terminal Alkynes with Boryldisiloxane
Authors: Zhou Hui , Wang Yan‐Bo
Published: August 2014

By employing 1,1,3,3‐tetramethyl‐1,3‐(pinacolboryl)disiloxane as a novel silicon source, the N‐heterocyclic carbene copper complex catalyzed hydrosilylation of terminal alkynes was developed to prepare vinyldisiloxanes in a highly regio‐ and stereoselective manner. A number of functional groups, including ether, ester, cyano, nitro, halo, hydroxyl, cyclopropyl, and aryl groups, were tolerated under the optimized conditions. A mechanistic investigation was undertaken by using density functional theory calculations. This approach allows facile entry to unsymmetrical disubstituted (E)‐alkenes by Pd‐catalyzed cross‐coupling reactions.
Minimizing Polysulfide Shuttles in Lithium Sulfur Batteries by Introducing Immobile Lithium Ions into Carbon–Sulfur Nanocomposites
Authors: Cai Weiwei , Li Jing , Zhang Yunfeng , Xu Guodong , Cheng Hansong
Published: August 2014

A facile synthesis of a carbon–sulfur nanocomposite, of which the capacity retention ratio is substantially enhanced by almost 100 %, is presented for polysulfide shuttle reduction in lithium sulfur batteries through the introduction of immobile lithium‐ion sites into the composite. A commercial Nafion ionomer, which can reduce thiosulfate sodium to sulfur in situ, owing to its acidity, provides immobile lithium ions after lithium exchange in the nanocomposite to attract the negatively charged polysulfide species for reduction during discharge. The capacity decay of the second cycle discharge, which is about 25 % of the value for a conventional carbon–sulfur composite, is reduced to about 3 % by introducing Nafion into the nanocomposite, and the capacity retention of this novel carbon–Nafion–sulfur nanocomposite is improved by more than 100 % during long‐term battery operation.
DMAP‐BODIPY Alkynes: A Convenient Tool for Labeling Biomolecules for Bimodal PET–Optical Imaging
Authors: Brizet Bertrand , Goncalves Victor , Bernhard Claire , Harvey Pierre D. , Denat Franck , Goze Christine
Published: August 2014

Several new boron dipyrromethene/N,N‐dimethylaminopyridine (BODIPY‐DMAP) assemblies were synthesized as precursors for bimodal imaging probes (optical imaging, OI/positron emission tomography, PET). The photophysical properties of the new compounds were also studied. The first proof‐of‐concept was obtained with the preparation of several new BODIPY‐labeled bombesins and evaluation of the affinity for bombesin receptors by using a competition binding assay. Fluorination reactions were investigated on DMAP‐BODIPY precursors as well as on DMAP‐BODIPY‐labeled bombesins. Chemical modifications on the BODIPY core were also performed to obtain luminescent dyes emitting in the therapeutic window (650–900 nm), suitable for in vivo imaging, making these compounds promising precursors for PET/optical dual‐modality imaging agents.
Small Molecule Activation by POCOP‐Nickel Complexes
Authors: Hao Jingjun , Vabre Boris , Mougang‐Soumé Berline , Zargarian Davit
Published: August 2014

This contribution describes the reactivities of CO2, CO, O2, and ArNC with the pincer‐type complexes [(κP,κC,κP′‐POCOP)NiX] (POCOP=(R2POCH2)2CH; R=iPr; X=OSiMe3, NArH; Ar=2,6‐iPr2C6H3). Reaction of the amido derivative with CO2 and CO leads to a simple insertion into the NiN bond to give stable carbamate and carbamoyl derivatives, respectively, the pincer ligand backbone remaining intact in both cases. In contrast, the analogous reactions with the siloxide derivative produced kinetically labile insertion products that either revert to the starting material (in the case of CO2) or react further to give the mixed‐valent, dinickel species [(POCOP)NiII{μ,κO,κP,κP′‐OCOCH(CH2CH2OPR2)2}Ni0(CO)2]. The zero‐valent center in the latter compound is ligated by a new ligand arising from transformation of the POCOP ligand backbone. The carbonylation and carboxylation of the siloxido derivative also produced minor quantities of a side‐product identified as the trinickel species, [{(η3‐allyl)Ni(μO,κP‐R2PO)2}2Ni], arising from total dismantling of the POCOP ligand. Similar reactivities were observed with isonitrile, ArNC: reaction with the siloxido derivative resulted in a complex sequence of steps involving initial insertion, a 1,3‐hydrogen shift, and an Arbuzov rearrangement to give [Ni(CNAr)4] and a methacrylamide based on fragments of the POCOP ligand. Oxygenation of the amido and siloxido derivatives led to the phosphinate derivative, [(POCOP)Ni(OP(O)R2)], arising from oxidative transformation of the original ligand frame; the reaction with the Ni‐NHAr derivative also gave ArHNP(O)R2 through a complex NP bond‐forming reaction.
Interpretation of NMR Relaxation as a Tool for Characterising the Adsorption Strength of Liquids inside Porous Materials
Authors: D'Agostino Carmine , Mitchell Jonathan , Mantle Michael D. , Gladden Lynn F.
Published: August 2014

Nuclear magnetic resonance (NMR) relaxation times are shown to provide a unique probe of adsorbate–adsorbent interactions in liquid‐saturated porous materials. A short theoretical analysis is presented, which shows that the ratio of the longitudinal to transverse relaxation times (T1/T2) is related to an adsorbate–adsorbent interaction energy, and we introduce a quantitative metric esurf (based on the relaxation time ratio) characterising the strength of this surface interaction. We then consider the interaction of water with a range of oxide surfaces (TiO2 anatase, TiO2 rutile, γ‐Al2O3, SiO2, θ‐Al2O3 and ZrO2) and show that esurf correlates with the strongest adsorption sites present, as determined by temperature programmed desorption (TPD). Thus we demonstrate that NMR relaxation measurements have a direct physical interpretation in terms of the characterisation of activation energy of desorption from the surface. Further, for a series of chemically similar solid materials, in this case a range of oxide materials, for which at least two calibration values are obtainable by TPD, the esurf parameter yields a direct estimate of the maximum activation energy of desorption from the surface. The results suggest that T1/T2 measurements may become a useful addition to the methods available to characterise liquid‐phase adsorption in porous materials. The particular motivation for this work is to characterise adsorbate–surface interactions in liquid‐phase catalysis.
Activation of Sulfur Dioxide by Bis[N,N′‐diisopropylbenzamidinato(−)]silicon(II): Synthesis of Neutral Six‐Coordinate Silicon(IV) Complexes with Chelating O,O′‐Sulfito or O,O′‐Dithionito Ligands
Authors: Junold Konstantin , Mück Felix M. , Kupper Claudia , Baus Johannes A. , Burschka Christian , Tacke Reinhold
Published: August 2014

The neutral six‐coordinate silicon(IV) complexes 2 and 3 (mixture of cis‐3 and trans‐3) were synthesized by reaction of the donor‐stabilized silylene bis[N,N′‐diisopropylbenzamidinato(−)]silicon(II) (1) with SO2. Compounds 2 and 3 are the first silicon(IV) complexes with chelating sulfito or dithionito ligands, and 3 is even the first molecular compound with a chelating dithionito ligand. Compounds 2 and 3 were structurally characterized by crystal structure analyses and multinuclear NMR spectroscopic studies in the solid state and in solution.
Macrocyclic Olefin Metathesis at High Concentrations by Using a Phase‐Separation Strategy
Authors: Raymond Michaël , Holtz‐Mulholland Michael , Collins Shawn K.
Published: August 2014

Macrocyclic olefin metathesis has seen advances in the areas of stereochemistry, chemoselectivity, and catalyst stability, but strategies aimed at controlling dilution effects in macrocyclizations are rare. Herein, a protocol to promote macrocyclic olefin metathesis, one of the most common synthetic tools used to prepare macrocycles, at relatively high concentrations (up to 60 mM) is described by exploitation of a phase‐separation strategy. A variety of macrocyclic skeletons could be prepared having either different alkyl, aryl, or amino acids spacers.
Mechanistic Insights into the Oxidative Coupling of N‐Heterocyclic Carbenes within the Coordination Sphere of Copper Complexes
Authors: Lake Benjamin R. M. , Ariafard Alireza , Willans Charlotte E.
Published: August 2014

The behavior of N‐heterocyclic carbene (NHC) ligands in organometallic chemistry is hugely important for catalysis, due to the effect of these ligands on catalytic pathways and their involvement in catalyst decomposition. In this report, a combined experimental and computational study is presented, which provides mechanistic understanding of the unprecedented oxidative coupling of NHCs at Cu. The presence of CuI–, CuII–, and CuIII–NHC complexes during the process is postulated, with the unusual Ccarbene–Ccarbene oxidative coupling reaction occurring under extremely mild reaction conditions. This process may represent a novel pathway for the decomposition of Cu–NHC complexes.
Cu(I)–NHC‐Catalyzed Silylation of Allenes: Diastereoselective Three‐Component Coupling with Aldehydes
Authors: Rae James , Hu Ya Chu , Procter David J.
Published: August 2014

Copper‐catalyzed silylation of aryl allenes using a silylborane reagent affords vinyl silane building blocks with high efficiency. The use of a seven‐membered NHC ligand proved crucial for high regioselectivity. The catalytically generated allylcoppper intermediates were intercepted by aldehydes in a diastereoselective three‐component coupling to furnish homoallylic alcohols.
ChemInform Abstract: A Photo‐Reagent System of Benzimidazoline and Ru(bpy)3Cl2 to Promote Hexenyl Radical Cyclization and Dowd—Beckwith Ring‐Expansion of α‐Halomethyl‐Substituted Benzocyclic 1‐Alkanones.
Authors: Hasegawa Eietsu , Tateyama Minami , Hoshi Tsuneaki , Ohta Taku , Tayama Eiji , Iwamoto Hajime , Takizawa Shin‐ya , Murata Shigeru
Published: August 2014

A benzimidazoline ligand in combination with a Ru‐ or Ir‐complex promotes photoinduced electron‐transfer reactions of α‐halomethyl substituted substrates to form primary alkyl radicals via selective C‐halogen bond cleavage.
ChemInform Abstract: An Approach to the Synthesis of 7‐Amino‐6‐imino‐9‐phenyl‐6H‐benzo[c]chromene‐8‐carbonitrile Derivatives via a Three‐Component Reaction under Ultrasonic Irradiation.
Authors: Alizadeh Abdolali , Sedighian Hadi , Ghanbaripour Rashid
Published: August 2014

Polysubstituted benzene derivatives (IV) and (VII) are obtained by a simple three‐component one‐pot reaction of salicylaldehydes, malononitrile, and 2‐(1‐arylethylidene)malononitrile.
ChemInform Abstract: Reductive Cross‐Coupling Reactions Between Two Electrophiles
Authors: Knappke Christiane E. I. , Grupe Sabine , Gaertner Dominik , Corpet Martin , Gosmini Corinne , Jacobi von Wangelin Axel
Published: August 2014

Review: [state of the art, recent protocols and important mechanistic studies; 50 refs.
ChemInform Abstract: Environmentally‐Benign Catalysts for the Selective Catalytic Reduction of NOx from Diesel Engines: Structure—Activity Relationship and Reaction Mechanism Aspects
Authors: Liu Fudong , Yu Yunbo , He Hong
Published: August 2014

Review: 219 refs.
Synthesis and Structure–Activity Relationship Studies of 2‐(1,3,4‐Oxadiazole‐2(3H)‐thione)‐3‐amino‐5‐arylthieno[2,3‐b]pyridines as Inhibitors of DRAK2
Authors: Leonczak Piotr , Gao Ling‐Jie , Ramadori Anna Teresa , Lescrinier Eveline , Rozenski Jef , De Jonghe Steven , Herdewijn Piet
Published: August 2014

In recent years, DAPK‐related apoptosis‐inducing protein kinase 2 (DRAK2) has emerged as a promising target for the treatment of a variety of autoimmune diseases and for the prevention of graft rejection after organ transplantation. However, medicinal chemistry optimization campaigns for the discovery of novel small‐molecule inhibitors of DRAK2 have not yet been published. Screening of a proprietary compound library led to the discovery of a benzothiophene analogue that displays an affinity constant (Kd) value of 0.25 μM. Variation of the core scaffold and of the substitution pattern afforded a series of 5‐arylthieno[2,3‐b]pyridines with strong binding affinity (Kd=0.008 μM for the most potent representative). These compounds also show promising activity in a functional biochemical DRAK2 enzyme assay, with an IC50 value of 0.029 μM for the most potent congener. Selectivity profiling of the most potent compounds revealed that they lack selectivity within the DAPK family of kinases. However, one of the less potent analogues is a selective ligand for DRAK2 and can be used as starting point for the synthesis of selective and potent DRAK2 inhibitors.
Design and Synthesis of Aminostilbene–Arylpropenones as Tubulin Polymerization Inhibitors
Authors: Kamal Ahmed , Kumar G. Bharath , Polepalli Sowjanya , Shaik Anver Basha , Reddy Vangala Santhosh , Reddy M. Kashi , Reddy Ch. Ratna , Mahesh Rasala , Kapure Jeevak Sopanrao , Jain Nishant
Published: August 2014

A series of aminostilbene—arylpropenones were designed and synthesized by Michael addition and were investigated for their cytotoxic activity against various human cancer cell lines. Some of the investigated compounds exhibited significant antiproliferative activity against a panel of 60 human cancer cell lines of the US National Cancer Institute, with 50 % growth inhibition (GI50) values in the range from <0.01 to 19.9 μM. One of the compounds showed a broad spectrum of antiproliferative efficacy on most of the cell lines, with a GI50 value of <0.01 μM. All of the synthesized compounds displayed cytotoxicity against A549 (non‐small‐cell lung cancer), HeLa (cervical carcinoma), MCF‐7 (breast cancer), and HCT116 (colon carcinoma) with 50 % inhibitory concentration (IC50) values ranging from 0.011 to 8.56 μM. A cell cycle assay revealed that these compounds arrested the G2/M phase of the cell cycle. Two compounds exhibited strong inhibitory effects on tubulin assembly with IC50 values of 0.71 and 0.79 μM. Moreover, dot‐blot analysis of cyclin B1 demonstrated that some of the congeners strongly induced cyclin B1 protein levels. Molecular docking studies indicated that these compounds occupy the colchicine binding site of tubulin.
Using distributed memory parallel computers and GPU clusters for multidimensional Monte Carlo integration
Authors: Szałkowski Dominik , Stpiczyński Przemysław
Published: August 2014

The aim of this paper is to show that the multidimensional Monte Carlo integration can be efficiently implemented on various distributed memory parallel computers and clusters of multicore nodes using recently developed parallel versions of linear congruential generator and lagged Fibonacci generator pseudorandom number generators. We show how to accelerate the overall performance by offloading some computations to Graphics Processing Units (GPUs), and we discuss how to transform Message Passing Interface (MPI) + OpenMP programs to MPI + OpenMP + CUDA model. We explain how to utilize multiple cores of CPUs together with multiple GPU accelerators within a single node and how to achieve reasonable load balancing of all computational resources of GPU‐accelerated multicore nodes. We present and discuss the results of experiments performed on the following target architectures: IBM Blue Gene/Q parallel computer, a cluster of Intel Xeon E5‐2660 servers, and a Tesla‐based GPU cluster with Intel Xeon X5650 multicore processors. The results are presented from two points of view: strong scaling and weak scaling. We also compare the performance of all considered architectures. Copyright © 2014 John Wiley & Sons, Ltd.
Nanostructuring of Self‐Assembled Porphyrin Networks at a Solid/Liquid Interface: Local Manipulation under Global Control
Authors: Coenen Michiel J. J. , Khoury Tony , Crossley Maxwell J. , Hendriksen Bas L. M. , Elemans Johannes A. A. W. , Speller Sylvia
Published: August 2014

Molecules of (5,10,15,20‐tetraundecylporphyrinato)‐copper(II) [(TUP)Cu] can self‐assemble into four different polymorphs at the interface between highly oriented pyrolytic graphite and 1‐octanoic acid. Scanning tunneling microscopy (STM) reveals that it is possible to combine the global control over monolayer structure, provided by the composition and concentration of the supernatant solution, with local control, from nanomanipulation by the STM tip. In the initially formed monolayer, with a polymorph composition governed by the concentration of (TUP)Cu in the supernatant solution, the exchange of molecules physisorbed at the solid/liquid interface with those in the liquid is very limited. By using a nanoshaving procedure at the tip, defects are created in the monolayer, and these serve as local manipulation sites to create domains of higher or lower molecular density, and to incorporate a second molecular species, (TUP)Co into the monolayer of (TUP)Cu.
Light‐Accelerated Biocatalytic Oxidation Reactions
Authors: Kochius Svenja , Ni Yan , Kara Selin , Gargiulo Serena , Schrader Jens , Holtmann Dirk , Hollmann Frank
Published: August 2014

The influence of (visible) light on the performance of laccase mediator systems (LMS) was investigated. As a model reaction, LMS‐mediated nicotinamide adenine dinucleotide (NAD+) regeneration to promote alcohol dehydrogenase catalyzed oxidation reactions was examined.
Engineering the Electrochemical Capacitive Properties of Graphene Sheets in Ionic‐Liquid Electrolytes by Correct Selection of Anions
Authors: Shi Minjie , Kou Shengzhong , Yan Xingbin
Published: August 2014

Graphene sheet (GS)–ionic liquid (IL) supercapacitors are receiving intense interest because their specific energy density far exceeds that of GS–aqueous electrolytes supercapacitors. The electrochemical properties of ILs mainly depend on their diverse ions, especially anions. Therefore, identifying suitable IL electrolytes for GSs is currently one of the most important tasks. The electrochemical behavior of GSs in a series of ILs composed of 1‐ethyl‐3‐methylimidazolium cation (EMIM+) with different anions is systematically studied. Combined with the formula derivation and building models, it is shown that the viscosity, ion size, and molecular weight of ILs affect the electrical conductivity of ILs, and thus, determine the electrochemical performances of GSs. Because the EMIM–dicyanamide IL has the lowest viscosity, ion size, and molecular weight, GSs in it exhibit the highest specific capacitance, smallest resistance, and best rate capability. In addition, because the tetrafluoroborate anion (BF4−) has the best electrochemical stability, the GS–[EMIM][BF4] supercapacitor has the widest potential window, and thus, displays the largest energy density. These results may provide valuable information for selecting appropriate ILs and designing high‐performance GS–IL supercapacitors to meet different needs.
Panmixia defines the genetic diversity of a unique arthropod‐dispersed fungus specific to Protea flowers
Authors: Aylward Janneke , Dreyer Léanne L. , Steenkamp Emma T. , Wingfield Michael J. , Roets Francois
Published: August 2014

Knoxdaviesia proteae, a fungus specific to the floral structures of the iconic Cape Floral Kingdom plant, Protea repens, is dispersed by mites phoretic on beetles that pollinate these flowers. Although the vectors of K. proteae have been identified, little is known regarding its patterns of distribution. Seed bearing infructescences of P. repens were sampled from current and previous flowering seasons, from which K. proteae individuals were isolated and cultured. The genotypes of K. proteae isolates were determined using 12 microsatellite markers specific to this species. Genetic diversity indices showed a high level of similarity between K. proteae isolates from the two different infructescence age classes. The heterozygosity of the population was high (0.74 ± 0.04), and exceptional genotypic diversity was encountered (Ĝ = 97.87%). Population differentiation was negligible, owing to the numerous migrants between the infructescence age classes (Nm = 47.83) and between P. repens trees (Nm = 2.96). Parsimony analysis revealed interconnected genotypes, indicative of recombination and homoplasies, and the index of linkage disequilibrium confirmed that outcrossing is prevalent in K. proteae ( = 0.0067; P = 0.132). The high diversity and panmixia in this population is likely a result of regular gene flow and an outcrossing reproductive strategy. The lack of genetic cohesion between individuals from a single P. repens tree suggests that K. proteae dispersal does not primarily occur over short distances via mites as hypothesized, but rather that long‐distance dispersal by beetles plays an important part in the biology of these intriguing fungi.
Integrative tracking methods elucidate the evolutionary dynamics of a migratory divide
Authors: Alvarado Allison H. , Fuller Trevon L. , Smith Thomas B.
Published: August 2014

Migratory divides, the boundary between adjacent bird populations that migrate in different directions, are of considerable interest to evolutionary biologists because of their alleged role in speciation of migratory birds. However, the small size of many passerines has traditionally limited the tools available to track populations and as a result, restricted our ability to study how reproductive isolation might occur across a divide. Here, we integrate multiple approaches by using genetic, geolocator, and morphological data to investigate a migratory divide in hermit thrushes (Catharus guttatus). First, high genetic divergence between migratory groups indicates the divide is a region of secondary contact between historically isolated populations. Second, despite low sample sizes, geolocators reveal dramatic differences in overwintering locations and migratory distance of individuals from either side of the divide. Third, a diagnostic genetic marker that proved useful for tracking a key population suggests a likely intermediate nonbreeding location of birds from the hybrid zone. This finding, combined with lower return rates from this region, is consistent with comparatively lower fitness of hybrids, which is possibly due to this intermediate migration pattern. We discuss our results in the context of reproductive isolating mechanisms associated with migration patterns that have long been hypothesized to promote divergence across migratory divides.
Effects of structured heart failure disease management on mortality and morbidity depend on patients' mood: results from the Interdisciplinary Network for Heart Failure Study
Authors: Gelbrich Götz , Störk Stefan , Kreißl‐Kemmer Sonja , Faller Hermann , Prettin Christiane , Heuschmann Peter U. , Ertl Georg , Angermann Christiane E.
Published: August 2014

Aims

Depression is common in heart failure (HF) and associated with adverse outcomes. Randomized comparisons of the effectiveness of HF care strategies by patients' mood are scarce. We therefore investigated in a randomized trial a structured collaborative disease management programme (HeartNetCare‐HF™; HNC) recording mortality, morbidity, and symptoms in patients enrolled after hospitalization for decompensated systolic HF according to their responses to the 9‐item Patient Health Questionnaire (PHQ‐9) during an observation period of 180 days.

Methods and results

Subjects scoring <12/≥12 were categorized as non‐depressed/depressed, and those ignoring the questionnaire as PHQ‐deniers. Amongst 715 participants (69 ± 12 years, 29% female), 141 (20%) were depressed, 466 (65%) non‐depressed, and 108 (15%) PHQ‐deniers. The composite endpoint of mortality and re‐hospitalization was neutral overall and in all subgroups. However, HNC reduced mortality risk in both depressed and non‐depressed patients [adjusted hazard ratios (HRs) 0.12, 95% confidence interval (CI) 0.03–0.56, P = 0.006, and 0.49, 95% CI 0.25–0.93, P = 0.03, respectively], but not in PHQ‐deniers (HR 1.74, 95% CI 0.77–3.96, P = 0.19; P = 0.006 for homogeneity of HRs). Average frequencies of patient contacts in the HNC arm were 12.8 ± 7.9 in non‐depressed patients, 12.4 ± 7.1 in depressed patients, and 5.5 ± 7.2 in PHQ‐deniers (P < 0.001).

Conclusions

Early after decompensation, HNC reduced mortality risk in non‐depressed and even more in depressed subjects, but not in PHQ‐deniers. This suggests that differential acceptability and chance of success of care strategies such as HNC might be predicted by appropriate assessment of patients' baseline characteristics including psychological disposition. These post‐hoc results should be reassessed by prospective evaluation of HNC in larger HF populations.
Bone morphogenetic protein 4 inhibits liposaccharide‐induced inflammation in the airway
Authors: Li Zhengtu , Wang Jian , Wang Yan , Jiang Hua , Xu Xiaoming , Zhang Chenting , Li Defu , Xu Chuyi , Zhang Kedong , Qi Yafei , Gong Xuefang , Tang Chun , Zhong Nanshan , Lu Wenju
Published: August 2014

Bone morphogenetic protein 4 (BMP4) is a multifunctional growth factor that belongs to the TGF‐β superfamily. The role of BMP4 in lung diseases is not fully understood. Here, we demonstrate that BMP4 was upregulated in lungs undergoing lipopolysaccharide (LPS)‐induced inflammation, and in airway epithelial cells treated with LPS or TNF‐α. BMP4 mutant (BMP4+/−) mice presented with more severe lung inflammation in response to LPS or Pseudomonas aeruginosa, and lower bacterial load compared with that in BMP4+/+ mice. Knockdown of BMP4 by siRNA increased LPS and TNF‐α‐induced IL‐8 expression in 16HBE human airway epithelial cells and in primary human bronchial epithelial cells. Similarly, peritoneal macrophages from BMP4+/− mice produced greater levels of TNF‐α and keratinocyte chemoattractant (KC) upon LPS treatment compared with cells from BMP4+/+ mice. Administration of exogenous BMP4 attenuated the upregulation of TNF‐α, IL‐8, or KC induced by LPS and/or TNF‐α in airway epithelial cells, and peritoneal macrophages. Finally, partial deficiency of BMP4 in BMP4+/− mice protected the animals from restrictive lung function reduction upon chronic LPS exposure. These results indicate that BMP4 plays an important anti‐inflammatory role, controlling the strength and facilitating the resolution of acute lung inflammation; yet, BMP4 also contributes to lung function impairment during chronic lung inflammation.
Th17‐related cytokines contribute to recall‐like expansion/effector function of HMBPP‐specific Vγ2Vδ2 T cells after Mycobacterium tuberculosis infection or vaccination
Authors: Shen Hongbo , Wang Yunqi , Chen Crystal Y. , Frencher James , Huang Dan , Yang Enzhuo , Ryan‐Payseur Bridgett , Chen Zheng W.
Published: August 2014

Whether cytokines can influence the adaptive immune response by antigen‐specific γδ T cells during infections or vaccinations remains unknown. We previously demonstrated that, during BCG/Mycobacterium tuberculosis (Mtb) infections, Th17‐related cytokines markedly upregulated when phosphoantigen‐specific Vγ2Vδ2 T cells expanded. In this study, we examined the involvement of Th17‐related cytokines in the recall‐like responses of Vγ2Vδ2 T cells following Mtb infection or vaccination against TB. Treatment with IL‐17A/IL‐17F or IL‐22 expanded phosphoantigen 4‐hydroxy‐3‐methyl‐but‐enyl pyrophosphate (HMBPP)‐stimulated Vγ2Vδ2 T cells from BCG‐vaccinated macaques but not from naïve animals, and IL‐23 induced greater expansion than the other Th17‐related cytokines. Consistently, Mtb infection of macaques also enhanced the ability of IL‐17/IL‐22 or IL‐23 to expand HMBPP‐stimulated Vγ2Vδ2 T cells. When evaluating IL‐23 signaling as a prototype, we found that HMBPP/IL‐23‐expanded Vγ2Vδ2 T cells from macaques infected with Mtb or vaccinated with BCG or Listeria ΔactA prfA*‐ESAT6/Ag85B produced IL‐17, IL‐22, IL‐2, and IFN‐γ. Interestingly, HMBPP/IL‐23‐induced production of IFN‐γ in turn facilitated IL‐23‐induced expansion of HMBPP‐activated Vγ2Vδ2 T cells. Furthermore, HMBPP/IL‐23‐induced proliferation of Vγ2Vδ2 T cells appeared to require APC contact and involve the conventional and novel protein kinase C signaling pathways. These findings suggest that Th17‐related cytokines can contribute to recall‐like expansion and effector function of Ag‐specific γδ T cells after infection or vaccination.
IL‐15‐dependent CD8+CD122+ T cells ameliorate experimental autoimmune encephalomyelitis by modulating IL‐17 production by CD4+ T cells
Authors: Yu Ping , Bamford Richard N. , Waldmann Thomas A.
Published: August 2014

Interleukin‐15 (IL‐15) is an inflammatory cytokine whose role in autoimmune diseases has not been fully elucidated. Th17 cells have been shown to play critical roles in experimental autoimmune encephalomyelitis (EAE) models. In this study, we demonstrate that blockade of IL‐15 signaling by TMβ‐1 mAb treatment aggravated EAE severity. The key mechanism was not NK‐cell depletion but depletion of CD8+CD122+ T cells. Adoptive transfer of exogenous CD8+CD122+ T cells to TMβ‐1‐treated mice rescued animals from severe disease. Moreover, transfer of preactivated CD8+CD122+ T cells prevented EAE development and significantly reduced IL‐17 secretion. Naïve effector CD4+CD25− T cells cultured with either CD8+CD122+ T cells from wild‐type mice or IL‐15 transgenic mice displayed lower frequencies of IL‐17A production with lower amounts of IL‐17 in the supernatants when compared with production by effector CD4+CD25− T cells cultured alone. Addition of a neutralizing antibody to IL‐10 led to recovery of IL‐17A production in Th17 cultures. Furthermore, coculture of CD8+CD122+ T cells with effector CD4+ T cells inhibited their proliferation significantly, suggesting a regulatory function for IL‐15 dependent CD8+CD122+ T cells. Taken together, these observations suggest that IL‐15, acting through CD8+CD122+ T cells, has a negative regulatory role in reducing IL‐17 production and Th17‐mediated EAE inflammation.
Insight into Structure: Function Relationships in a Molecular Spin‐Crossover Crystal, from a Related Weakly Cooperative Compound
Authors: Elhaïk Jérôme , Kilner Colin A. , Halcrow Malcolm A.
Published: August 2014

The ClO4– salt of [FeL2]2+ {L = 2,6‐bis(3‐methylpyrazol‐1‐yl)pyridine} undergoes very gradual thermal spin‐crossover centered just below room temperature. In contrast, the BF4– salt of the same complex exhibits an abrupt and structured spin‐transition at lower temperature, with a complicated structural chemistry. The difference can be attributed to a much larger change in molecular structure between the spin states of the complex in the more cooperative BF4– salt, leading to an increased kinetic barrier for their interconversion. Consistent with that suggestion, the high‐spin and low‐spin structures of weakly cooperative [FeL2][ClO4]2 are almost superimposable.
Flexible Synthesis of Planar Chiral Azoninones and Optically Active Indolizidinones
Authors: Bohland Frank , Erlin Irina , Platte Lukas , Schröder Maike , Schollmeyer Dieter , Nubbemeyer Udo
Published: August 2014

The flexible synthesis of defined substituted optically active indolizidinones starting from chiral pool (S)‐proline and trans 4‐hydroxy‐(S)‐proline is described. Several defined 2‐vinylpyrrolidines were generated in short sequences. The aza‐Claisen rearrangement using chloro and phenylketene equivalents delivered nine‐membered‐ring lactams with up to three stereogenic centres and pS‐arranged E olefins. Depending on the substitution pattern, certain azoninones had a flexible conformation and showed pS/pR double‐bond flipping. Treatment of the unsaturated lactams with the soft electrophile iodine induced diastereoselective transannular ring contractions. Here, the planar chiral arrangement of the azoninone double bond predetermined the bridgehead configuration of the product indolizidinones. Thus, the (S)‐proline starting materials could be used to gain access to either one of the two antipodal series of indolizidinone products. The indolizidinone scaffolds should serve as versatile key intermediates in the synthesis of natural products and pharmaceutically important molecules.
Assessment of high resolution melting analysis as a potential SNP genotyping technique in forensic casework
Authors: Venables Samantha J. , Mehta Bhavik , Daniel Runa , Walsh Simon J. , van Oorschot Roland A. H. , McNevin Dennis
Published: August 2014

High resolution melting (HRM) analysis is a simple, cost effective, closed tube SNP genotyping technique with high throughput potential. The effectiveness of HRM for forensic SNP genotyping was assessed with five commercially available HRM kits evaluated on the ViiA™ 7 Real Time PCR instrument. Four kits performed satisfactorily against forensically relevant criteria. One was further assessed to determine the sensitivity, reproducibility, and accuracy of HRM SNP genotyping. The manufacturer's protocol using 0.5 ng input DNA and 45 PCR cycles produced accurate and reproducible results for 17 of the 19 SNPs examined. Problematic SNPs had GC rich flanking regions which introduced additional melting domains into the melting curve (rs1800407) or included homozygotes that were difficult to distinguish reliably (rs16891982; a G to C SNP). A proof of concept multiplexing experiment revealed that multiplexing a small number of SNPs may be possible after further investigation. HRM enables genotyping of a number of SNPs in a large number of samples without extensive optimization. However, it requires more genomic DNA as template in comparison to SNaPshot®. Furthermore, suitably modifying pre‐existing forensic intelligence SNP panels for HRM analysis may pose difficulties due to the properties of some SNPs.
Optimization of STR locus enrichment for STR profiling of fragmented DNA
Authors: Ham Seon‐Kyu , Kim Se‐Yong , Ahn Jang‐Won , Seo Bo Young , Woo Kwang‐Man , Choi Cheol Yong , Lee Seung‐Hwan
Published: August 2014

DNA degradation is a major obstacle in gaining an accurate profile with standard DNA typing technology. Although alternative genotyping strategies such as mini‐STRs and SNPs have proven to be more successful in profiling degraded DNA, these approaches also have limitations. Here, we show that locus enrichment by hybridization of degraded genomic DNA with an STR locus‐specific biotinylated oligonucleotide is a powerful approach to overcome problems in STR typing of highly degraded DNA. An experimental investigation of factors affecting the efficiency of this method indicates that the choice of primer and molar ratio of primers to genomic DNA are critical factors in improving enrichment of the STR locus before genotyping with multiplex kits. In addition, we find that indirect capture rather than direct capture with magnetic beads yields better enrichment efficiency for STR locus enrichments. Using these strategies, we demonstrate an improvement in STR typing of DNA from cultured cells damaged by exposure to sunlight or UV. We suggest that this approach could be applied to highly degraded forensic samples alone or in combination with mini‐STRs.
Differential detection of Rhizoma coptidis by capillary electrophoresis electrospray ionization mass spectrometry with a nanospray interface
Authors: Liu Jing‐Xin , Zhang Yi‐Wei , Yuan Fang , Chen Hong‐Xu , Zhang Xin‐Xiang
Published: August 2014

A lab prototype CE‐nanospray‐MS platform with a high sensitivity porous sprayer was successfully applied in differential identification of Rhizoma coptidis in this paper. To obtain a stable and reliable nanospray, detailed optimizations about emitter geometry, buffer composition, emitter position, and spray voltage, as well as emitter cleanliness were discussed. Results showed that the reproducibility and sensitivity for separations of alkaloid standards were satisfactory using CE‐nanospray‐MS, which were also compared to ultra‐HPLC (UHPLC)‐MS. Their signal responds were at the same order of magnitude (intensities: 0.8 − 1.5 × 108 vs. 3.8 − 6.2 × 108), even though a 2 nL injection for CE was 2500‐fold lower than UHPLC (5 μL injection). The absolute LOD results of CE‐MS showed a remarkable superiority (18–24 fg), equal to 1000‐fold lower than that of UHPLC‐MS. Principal component analysis (PCA) of adulterated R. coptidis showed that this protocol had the ability to profile and qualify complex herb medicines, which also created a great potential for evaluation and qualification of rare and valuable Chinese medicines in future.
Lithiation of an Iron Oxide‐Based Anode for Stable, High‐Capacity Lithium‐Ion Batteries of Porous Carbon–Fe3O4/Li[Ni0.59Co0.16Mn0.25]O2
Authors: Ming Jun , Kwak Won Jin , Youn Sung Jun , Ming Hai , Hassoun Jusef , Sun Yang‐Kook
Published: August 2014

The lithium storage capacity of an iron oxide‐based anode of porous carbon–Fe3O4 (i.e., PC–Fe3O4) was investigated by varying the initial current and mass density of the electrode to achieve a good utilization coefficient of the oxide. It was confirmed that these factors largely affected the capacity of PC–Fe3O4 and a certain mass density of the electrode was key to achieve a high area capacity (μAh cm−2). Moreover, the chemical and electrochemical lithiation of PC–Fe3O4 were related to the lithiation time and pressure and both were both systemically studied. After optimization, a new battery of PC–Fe3O4/Li[Ni0.59Co0.16Mn0.25]O2 with a high area capacity of 748 μAh cm−2 (≈150 mAh g−1) and superior energy density of 483 Wh kg−1 (work voltage≈3.2 V) was developed. The battery showed reversible work ability in the rate window of 50–800 mA g−1, and also it could be charged/discharged for well over 1000 cycles with a capacity retention of 63.8 % under the high current value of 0.505 mA (current density, 50 mA g−1).
Transformation of P2S5 into a Solid Electrolyte with Ionic Conductivity at the Positive Composite Electrode of All‐Solid‐State Lithium–Sulfur Batteries
Authors: Nagata Hiroshi , Chikusa Yasuo
Published: August 2014

Battery performance of an all‐solid‐state lithium–sulfur (Li–S) cell with a P2S5‐based positive composite electrode was investigated in the absence of solid electrolyte at the positive composite electrode. In the positive composite electrode, P2S5 without ionic conductivity was transformed into a solid electrolyte with ionic conductivity by incorporating lithium ions into P2S5 during the first charge–discharge cycle. Therefore, the all‐solid‐state Li–S cell with P2S5‐based positive composite electrode behaved as a secondary battery. This positive composite electrode is very low cost because it did not use an expensive solid electrolyte. In addition to using a cost‐effective positive composite electrode with a sulfur content of 60 wt %, the all‐solid‐state Li–S cell exhibited an extremely high capacity of 1042 mAh g−1 under 6.4 mA cm−2 at 25 °C.
A High‐Capacity Tellurium@Carbon Anode Material for Lithium‐Ion Batteries
Authors: Zhang Juan , Yin Ya‐Xia , You Ya , Yan Yang , Guo Yu‐Guo
Published: August 2014

The electrochemical properties of helical‐chain Ten molecules confined in a microporous carbon host (MPC) are reported here, showing potential as an attractive anode for Lithium‐ion batteries. These confined Ten molecules provide a high reversible volumetric capacity of 2558 mAh cm−3, with a redox potential of 1.5 V (vs. Li+/Li) (≈4.2 times higher than that of a Li4Ti5O12 anode, 613 mAh cm−3, 1.55 V vs. Li+/Li). The anode also exhibits an excellent high‐rate capability (998 mAh cm−3 at 10 C) and admirable long‐term cyclic stability (capacity retention of 85 % over 1000 cycles), benefiting from the good confinement of the MPC host and intrinsically superior conductivity of Ten chains inside it. Furthermore, a new type of Li‐ion full cell is successfully constructed with this tellurium@carbon anode and a traditional LiMn0.33Ni0.33Co0.33O2 cathode, which shows outstanding performance. All these unique merits show promise for the tellurium‐molecule‐based material as an attractive anode for building next‐generation Li‐ion batteries with high energy density and safe operation.
Thermal degradation of epoxy resin/carbon fiber composites: Influence of carbon fiber fraction on the fire reaction properties and on the gaseous species release
Authors: Dao Duy Quang , Rogaume Thomas , Luche Jocelyn , Richard Frank , Bustamante Valencia Lucas , Ruban Sindonie
Published: August 2014

The thermal degradation of epoxy resin/carbon fiber composites has been performed in ISO 5660 standard cone calorimeter using a piloted ignition. Two kinds of composites that differ by their volume fractions in carbon fiber (56 and 59 vol.%) were tested in this study. The cone calorimeter irradiance level was increased up to 75 kW m−2 to characterize the carbon fiber volume fraction influence on the composite thermal degradation. Thus, main flammability and combustibility parameters were determined and calculated such as mass loss, mass loss rate, ignition time, thermal response parameter, ignition temperature, thermal inertia, and heat of gasification. As a result, all the characteristic parameters for the thermal resistance of composites were decreased when the carbon fiber volume fraction increased. Moreover, the main gaseous products (such as NO, CO, CO2, HCN, H2O, and lightweight hydrocarbons) emitted as well as the oxygen consumption during the composite thermal decomposition were also quantified simultaneously with a portable gas analyzer and a Fourier transform infrared spectrometer. The main species emission yields calculated from the gas analysis results increased slightly when the carbon fiber volume fraction was increased in the initial sample. The epoxy composite was represented as a sooty material with a significant production of soot particles during the combustion process. Furthermore, heat release rate, total heat release, and effective heat of combustion were calculated by using the oxygen consumption calorimetry technique. The results obtained showed that a small increasing of composite carbon fiber amount induced a sharp decrease of heat release rate and total heat release. Copyright © 2014 John Wiley & Sons, Ltd.
PSAT1 regulates cyclin D1 degradation and sustains proliferation of non‐small cell lung cancer cells
Authors: Yang Yi , Wu Jueheng , Cai Junchao , He Zhenjian , Yuan Jie , Zhu Xun , Li Yanbing , Li Mengfeng , Guan Hongyu
Published: August 2014

Multiple nodes in the one‐carbon metabolism pathway play important regulatory roles in cancer cell growth and tumorigenesis. The specific biological functions of metabolic enzymes in regulating the signaling pathways that are associated with tumor cell growth and survival, however, remain unclear. Our current study found that phosphoserine aminotransferase 1 (PSAT1), an enzyme catalyzing serine biosynthesis, was significantly up‐regulated in non‐small cell lung cancer (NSCLC) and was involved in the regulation of E2F activity. Loss‐ and gain‐of‐function experiments demonstrated that PSAT1 promoted cell cycle progression, cell proliferation and tumorigenesis. Mechanistic study suggested that elevated PSAT1 led to inhibition of cyclin D1 degradation and subsequently an alteration in Rb‐E2F pathway activity, which in turn enhanced G1 progression and proliferation of NSCLC cells. Moreover, phosphorylation of cyclin D1 at threonine 286 by GSK‐3β was required for PSAT1‐induced blockage of cyclin D1 degradation. We also found that the activity of p70S6K mediated the effects of PSAT1 on GSK‐3β phosphorylation and cyclin D1 degradation. We further identified that PSAT1 was over‐expressed in NSCLC and predicted poor clinical outcome of patients with the disease. Correlation analysis showed that PSAT1 expression positively correlated with the levels of phosphorylated GSK‐3β, cyclin D1 and phosphorylated Rb in NSCLC primary tumors. These findings uncover a mechanism for constitutive activation of E2F via which unrestrained cell cycle progression occurs in NSCLC and may represent a prognostic biomarker and therapeutic target.
MicroRNA‐155 deficiency enhances the recruitment and functions of myeloid‐derived suppressor cells in tumor microenvironment and promotes solid tumor growth
Authors: Wang Junfeng , Yu Fang , Jia Xuemei , Iwanowycz Stephen , Wang Yuzhen , Huang Shiang , Ai Walden , Fan Daping
Published: August 2014

Immune cells in tumor microenvironment play a prominent role in tumor progression and metastasis. MicroRNA‐155 (miR‐155) represents an important player in innate and adaptive immunity by regulating differentiation, maturation and activation of macrophages, dendritic cells, B cells and T cells. However, the role of miR‐155 expression in immune cells in solid tumor development is less elucidated. Our current study showed that both B16‐F10 melanoma and Lewis lung carcinoma tumors grew much faster in bic/miR‐155 knockout (miR‐155−/−) mice along with an increase of myeloid‐derived suppressor cells (MDSCs) accumulation in tumors, compared to that in wild‐type mice. Bone marrow transplantation study showed that bone marrow miR‐155 deficiency could replicate the above tumor‐promoting phenotype. In vitro study demonstrated that tumor‐infiltrating miR‐155−/− MDSCs showed greater migration ability and expressed higher level of multiple chemokines. Furthermore, we found that the level of HIF‐1α, a direct target of miR‐155, was increased in miR‐155 deficient MDSCs, and that the increased HIF‐1α upregulated CXCL1, CXCL3 and CXCL8 expression in MDSCs, contributing to the enhanced recruitment of miR‐155−/− MDSCs to the tumors. Moreover, miR‐155−/− MDSCs showed enhanced immunosuppressive and pro‐angiogenic capacities. Taken together, our study, for the first time, demonstrated that miR‐155 deficiency promoted solid tumor growth through increasing the recruitment of MDSCs to tumor microenvironment and enhancing the tumor‐promoting functions of the recruited MDSCs. Thus, upregulating miR‐155 expression in MDSCs may be developed as a therapeutic approach to halt tumor development.
FURTHER STUDIES OF THE VALIDITY OF COMPONENTS OF THE U. S. NAVAL POSTGRADUATE SCHOOL TEST
Authors: Mollenkopf William G.
Published: August 2014

The U. S. Naval Postgraduate School Test, Form ZNP, was the outcome of a three‐year research program carried out by Educational Testing Service for the Naval Postgraduate School. During this three‐year period, three experimental batteries were developed and tried out at the School, with subsequent validation against criteria of academic success.

The operational test consists of Mathematics Aptitude, Advanced Mathematics, Physical Science and Engineering, Interpretation of Scientific Data, and Experimental Science sections. This report presents further information on the effectiveness of these sections for predicting success at the School, based on further validation of tests given in 1949 and 1950 which correspond to the sections of Form ZNP. (No direct validation of scores on Form ZNP is as yet possible, since at this date officers selected through its use have not yet entered the School.)

Two main outcomes of the study are (1) for the most part, results corroborate earlier findings as to test validity; and (2) the effectiveness of the tests given “in the fleet” in the fall of 1949 was considerably lower than when the same tests were given at the School.
LEVEL OF ASPIRATION MEASURES AND COLLEGE ACHIEVEMENT*
Authors: Schultz Douglas G. , Ricciuti Henry N.
Published: August 2014

The purpose of this study was to provide some indication as to the amount and kind of relationship between general college achievement and goal discrepancy scores derived from certain group level of aspiration techniques recently developed. Goal discrepancy scores for several groups of college students were derived from aspiration statements made in connection with two group experimental tests and with regular course examinations. These discrepancy scores were correlated with scores from a scholastic aptitude test and with Grade‐Point Average during the previous year at college. Partial correlation coefficients were computed between the goal discrepancy scores and Grade‐Point Average, holding scholastic aptitude scores constant.

There was no evidence uncovered to support the existence of a relationship between any of the goal discrepancy scores investigated and past academic achievement, whether or not scholastic aptitude is held constant. No curvilinear trends were discovered in the data. No consistent differences in the various correlations were apparent between aspiration instructions asking for expectations and instructions asking for goals.