bluuebunny/crossref_metadata_2025 huggingface dataset:
A bootstrap‐based method for optimal design of experiments
Authors: Paquet‐Durand O. , Zettel V. , Hitzmann B.
Published: August 2016

Bootstrapping can be used for the estimation of parameter variances, and it is straightforward to be implemented but computationally demanding compared with other methods for parameter error estimation. It is not bound to any restrictions such as the distribution of measurement errors. And because of the possible asymmetry of the probability densities of the parameters, the parameter estimation errors acquired by bootstrapping are likely to be more accurate.

In this work the feasibility of a bootstrap‐based method for optimal experimental design was evaluated for the Peleg model. The optimal design was performed, based on the Cramér‐Rao lower bound as a benchmark. Afterwards, the optimal design was calculated based on the bootstrap method.

It is demonstrated that a bootstrap‐based optimal design of experiments will give comparable results with the Cramér‐Rao lower bound optimal designs, however with slightly different measurement points in time. If the parameter errors obtained from both optimal experimental designs are compared, they deviate for the 2 methods on average by 1.5%.

Bootstrapping can be used for problems, which cannot be solved using Cramér‐Rao lower bound because of necessary but invalid assumptions. However, the benefits of the bootstrap method come at the cost of a significant increase in computational effort. Under similar conditions, the computation time for a bootstrap‐based optimal design was 25 minutes compared with 5 seconds when using the Cramér‐Rao lower bound method. As computers get faster and faster over time, the increase in computational demand will probably become less relevant in the future.
Cobalt Carbonate Hydroxide Nanowire Array on Ti Mesh: An Efficient and Robust 3D Catalyst for On‐Demand Hydrogen Generation from Alkaline NaBH4 Solution
Authors: Cui Liang , Sun Xuping , Xu Yuanhong , Yang Wenrong , Liu Jingquan
Published: August 2016

In this work, for the first time, a cobalt carbonate hydroxide (Co(CO3)0.5(OH)⋅0.11 H2O) nanowire array on Ti mesh (CHNA/Ti) was applied to drive the dehydrogenation of alkaline NaBH4 solution for on‐demand hydrogen production. Compared with other nanostructured Co‐based catalyst systems, CHNA/Ti can be activated more quickly and separated easily from fuel solutions. This self‐supported cobalt salt nanowire array catalyst works as an efficient and robust 3D catalyst for the hydrolysis reaction of NaBH4 with a hydrogen generation rate of 4000 mL min−1 gCo−1 and a low apparent activation energy of 39.78 kJ mol−1 and offers an attractive system for on‐demand hydrogen generation.
ChemInform Abstract: The Flexibility of P2O7 Dimers in Soft Structures: M2CdP2O7 (M: Rb, Cs).
Authors: Dong Xiaoyu , Shi Yunjing , Zhang Mingjie , Chen Zhaohui , Jing Qun , Yang Yun , Pan Shilie , Yang Zhihua , Li Hongyi
Published: August 2016

The new compounds Rb2CdP2O7 (I) and Cs2CdP2O7 (II) are prepared by calcination of stoichiometric mixtures of Rb2CO3 (Cs2CO3), CdO, and NH4H2PO4 (650 °C, 72 h).
ChemInform Abstract: An Octanuclear MnIII4DyIII4 Cluster Connected via Two μ5‐NO3‐ Bridges with Slow Relaxation of Magnetization.
Authors: Wang Feng , Peng Hua , Ding Yu
Published: August 2016

Dark brown crystals of [Mn4Dy4(mbm)14 (μ5‐NO3)2 (μ‐NO3)2(MeOH)2] (NO3)6·12H2O (mbm: (1‐methyl‐benzoimidazol‐2‐yl)methanolate) are obtained from 1:2 solutions of MeOH/MeCN containing Mn(ClO4)2, Dy(NO3)2, Hmbm, and triethylamine (25 °C, 14 d, 35% yield).
ChemInform Abstract: 3,6‐Di(pyridin‐2‐yl)‐1,2,4,5‐tetrazine (pytz) Mediated Metal‐Free Mild Oxidation of Thiols to Disulfides in Aqueous Medium.
Authors: Samanta Suvendu , Ray Shounak , Ghosh Abhisek Brata , Biswas Papu
Published: August 2016

A wide range of aromatic, aliphatic, and heterocyclic thiophenols are converted to the corresponding disulfides by a highly efficient metal free oxidation under neutral conditions.
ChemInform Abstract: N‐Picolinamides as Ligands for Ullmann‐Type C—N Coupling Reactions.
Authors: Damkaci Fehmi , Alawaed Abdulkhaliq , Vik Erik
Published: August 2016

The picolinamide ligand (NPP) in combination with Cu2O efficiently catalyzes the C—N coupling reaction between N‐heteroaryls and aryl halides or benzyl bromides.
ChemInform Abstract: Oxidative Trifluoromethylthiolation and Thiocyanation of Amines: A General Approach to N—S Bond Formation.
Authors: Xiong Heng‐Ying , Pannecoucke Xavier , Besset Tatiana
Published: August 2016

A practical and efficient one‐pot oxidative trifluoromethylthiolation of primary and secondary amines under mild conditions is presented.
ChemInform Abstract: A Facile and Rapid Preparation of Hydroxamic Acids by Hydroxylaminolysis Using DBU as Base.
Authors: Harris Craig S. , et al.
Published: August 2016

An efficient and robust hydroxylaminolysis of a wide range of complex carboxylic ester substrates using both DBU in solution and immobilized on a solid support is reported.
ChemInform Abstract: Copper‐Catalyzed Radical Coupling of 1,3‐Dicarbonyl Compounds with Terminal Alkenes for the Synthesis of Tetracarbonyl Compounds.
Authors: Zhang Mei‐Na , Zhao Mi‐Na , Chen Ming , Ren Zhi‐Hui , Wang Yao‐Yu , Guan Zheng‐Hui
Published: August 2016

Various functional groups are tolerated and only atmospheric air is used as oxidant.
ChemInform Abstract: Tunable Di‐ and Mono‐γ‐C—H Arylation of Phenylacetamides by Palladium‐Catalyzed Domino Reactions.
Authors: Liu Yunyun , Huang Bin , Cao Xiaoji , Wan Jie‐Ping
Published: August 2016

A selective ortho‐arylation of phenylacetamides is realized by a domino process consisting of installation of an in‐situ generated directing group and C—H arylation.
ChemInform Abstract: Stereospecific Synthesis of Unsymmetrical (E)‐ and (Z)‐1,2‐difluorostilbenes.
Authors: Lim Chongsoo , Wang Yi , Burton Donald J.
Published: August 2016

The title stilbenes are stereospecifically obtained using dioxane as solvent.
ChemInform Abstract: Palladium‐Catalyzed Ring Contraction Reaction of Naphthoquinones upon Reaction with Alkynes.
Authors: Wang Lei , Zhang Jianwei , Lang Ming , Wang Jian
Published: August 2016

A novel palladium catalyzed ring contraction reaction of naphthoquinones with alkynes is developed.
ChemInform Abstract: Three‐Component Access to 2‐Pyrrolin‐5‐ones and Their Use in Target‐Oriented and Diversity‐Oriented Synthesis.
Authors: Cores Angel , Estevez Veronica , Villacampa Mercedes , Menendez J. Carlos
Published: August 2016

New 2‐pyrrolin‐5‐ones (IV) are prepared by Hantzsch—type microwave‐assisted, solvent‐free sequential three‐component reaction of primary amines, β‐carbonyl compounds, and α‐bromoester and utilized e.g. as synthetic building blocks in a target‐oriented project for the synthesis of compound (VI) that is postulated as a candidate for HIV increase inhibition on the basis of computational studies.
ChemInform Abstract: The Pentadehydro‐Diels—Alder Reaction.
Authors: Wang Teng , Naredla Rajasekhar Reddy , Thompson Severin K. , Hoye Thomas R.
Published: August 2016

A new class of reaction is presented: the formal [4 + 2] cycloaddition of an allenyne moiety with a pendant alkyne or nitrile function to produce an α,3‐dehydro(aza)toluene intermediate of type (II), formed in the so‐called PDDA title reaction.
ChemInform Abstract: Solvent‐Free One‐Pot Synthesis of 2,2′‐Dithioxo‐[5,5′]bithiazolidinylidene‐4,4′‐diones.
Authors: Nasiri Farough , Zolali Amin , Asadbegi Sajad
Published: August 2016

The birhodanine derivatives are prepared under mild reaction conditions by three‐component reaction of various primary amines, CS2, and dimethyl acetylene dicarboxylate.
ChemInform Abstract: Regioselective Synthesis of 2‐Amino‐5‐(or 3‐)arylazo‐Substituted Pyridines and Pyrazines from Pyridinium N‐Aminides.
Authors: Gala Elena , Reyes M. Jose , Alvarez‐Builla Julio , Izquierdo M. Luisa
Published: August 2016

The title compounds bearing an arylazo group at the C‐3 or C‐5 position are regioselectively prepared from pyridinium N‐amidines.
ChemInform Abstract: A Simple and Efficient One‐Pot Synthesis of 1,4‐Dihydropyridines Using Nano‐WO3‐Supported Sulfonic Acid as an Heterogeneous Catalyst under Solvent‐Free Conditions.
Authors: Bitaraf Mehrnoosh , Amoozadeh Ali , Otokesh Somayeh
Published: August 2016

Aromatic aldehydes, β‐dicarbonyl compounds, and ammonium acetate afford the title pyridines in good to excellent yields under environmentally benign reaction conditions.
ChemInform Abstract: Cu(I)‐Catalyzed Double C—H Amination: Synthesis of 2‐Iodo‐imidazo[1,2‐a]pyridines.
Authors: Dheer Divya , Reddy K. Ranjith , Rath Santosh K. , Sangwan P. L. , Das Parthasarthi , Shankar Ravi
Published: August 2016

A variety of 2‐iodo‐imidazo[1,2‐a]pyridines (III) is synthesized by a copper‐catalyzed reaction of 2‐aminopyridines with terminal alkynes and iodine.
ChemInform Abstract: Cascade C—C and C—N Bond Formation: A Straightforward Synthesis of Phenanthridines and Fused Quinolines.
Authors: Borah Ashwini , Gogoi Pranjal
Published: August 2016

starting from various β‐chloro α,β‐unsaturated aldehydes or 2‐chloroaryl aldehydes
ChemInform Abstract: Alkali‐Metal‐Catalyzed Cross‐Dehydrogenative Couplings of Hydrosilanes with Amines.
Authors: Anga Srinivas , Sarazin Yann , Carpentier Jean‐Francois , Panda Tarun K.
Published: August 2016

The reaction is promoted by hexamethyldisilazides and the potassium derivative is the most effective one.
ChemInform Abstract: Total Synthesis of Cryptocaryol a by Enantioselective Iridium‐Catalyzed Alcohol C—H Allylation.
Authors: Perez Felix , Waldeck Andrew R. , Krische Michael J.
Published: August 2016

The polyketide natural product cryptocaryol A (I) is prepared in 8 steps via iridium catalyzed enantioselective diol double C—H allylation, which directly generates an acetate‐based triketide stereodiad.
ChemInform Abstract: C—H Functionalization on Carbohydrates
Authors: Frihed Tobias Gylling , Bols Mikael , Pedersen Christian Marcus
Published: August 2016

Review: [methods available for C—H functionalization in carbohydrate chemistry; 94 refs.
ChemInform Abstract: Concepts and Molecular Aspects in the Polypharmacology of PARP‐1 Inhibitors
Authors: Passeri Daniela , Camaioni Emidio , Liscio Paride , Sabbatini Paola , Ferri Martina , Carotti Andrea , Giacche Nicola , Pellicciari Roberto , Gioiello Antimo , Macchiarulo Antonio
Published: August 2016

Review: [52 refs.
ChemInform Abstract: Nucleotides and Nucleic Acids; Oligo‐ and Poly‐nucleotides as Sensors
Authors: Loakes David
Published: August 2016

Review: more than 1000 refs.
ChemInform Abstract: Nucleotides and Oligonucleotides: Mononucleotides
Authors: Narukulla Raman , Xu Yao‐Zhong
Published: August 2016

Review: synthesis, biological and medicinal application of nucleosides, DNA, and RNA posphonates and phosphoramidates
Dual polymer flocculants for mature fine tailings dewatering
Authors: Zhu Ying , Tan Xiaoli , Liu Qi
Published: August 2016

A cationic polymer, polydiallyldimethylammonium chloride (polyDADMAC), and an anionic (hydrolyzed) polyacrylamide (PAM), were used in sequence to treat the mature fine tailings (MFT) from the oil sands operations in Alberta, Canada. Capillary suction time (CST), specific resistance to filtration (SRF), and filter cake solid content were measured, and cryogenic scanning electron microscopic (cryo‐SEM) images of the MFT were taken, before and after the dual polymer treatment to evaluate the dewaterability of the MFT. The results were compared with treatment by a single polymer, which demonstrated that the dual polymer treatment resulted in improved dewaterability of the MFT due to the larger pore sizes.
CFD with population balance model to predict droplet size distribution in submerged turbulent multiphase jets
Authors: Rao Abhijit , Sathe Mayur , Reddy Rupesh K. , Nandakumar Krishnaswamy
Published: August 2016

During deepwater oil spill events, oil is released into a relatively stagnant environment (ocean water) in an uncontrolled manner. The oil phase initially emerges as a jet and the gushing oil loses its momentum energy and results in entrainment of surrounding water. The shear interaction between the oil mass and the ambient fluid results in generation of droplets with wide size distribution. In this study, we present a numerical model for predicting the droplet size distribution resulting from the interaction of turbulent oil jets with the surrounding quiescent environment. We achieve this objective by integrating traditional multiphase CFD models with a population balance approach. The developed model has been validated against the experimental observations reported in Johansen et al.[12] The ‘Mixture model’ has been employed for evaluating flow fields in the system. We restrict our study to the atomization regime, where the droplet disintegration process has a greater significance over the competing coalescence mechanism. The population balance equation has been solved using the ‘Class method’ and the disintegration of droplets has been modelled by including the breakage kernel suggested by Lehr.27 The developed model has been used to analyze the effect of dispersed (oil) phase flow rates, the presence of dispersants, and the presence of air in the jet phase on the overall size distribution of oil droplets. We also present a case which compares the droplet size distributions obtained by using the flow field evaluated by a more rigorous Eulerian Two‐Fluid model over Mixture model.
Descending projections from the inferior colliculus to the dorsal cochlear nucleus are excitatory
Authors: Milinkeviciute Giedre , Muniak Michael A. , Ryugo David K.
Published: August 2016

Ascending projections of the dorsal cochlear nucleus (DCN) target primarily the contralateral inferior colliculus (IC). In turn, the IC sends bilateral descending projections back to the DCN. We sought to determine the nature of these descending axons in order to infer circuit mechanisms of signal processing at one of the earliest stages of the central auditory pathway. An anterograde tracer was injected in the IC of CBA/Ca mice to reveal terminal characteristics of the descending axons. Retrograde tracer deposits were made in the DCN of CBA/Ca and transgenic GAD67–EGFP mice to investigate the cells giving rise to these projections. A multiunit best frequency was determined for each injection site. Brains were processed by using standard histologic methods for visualization and examined by fluorescent, brightfield, and electron microscopy. Descending projections from the IC were inferred to be excitatory because the cell bodies of retrogradely labeled neurons did not colabel with EGFP expression in neurons of GAD67–EGFP mice. Furthermore, additional experiments yielded no glycinergic or cholinergic positive cells in the IC, and descending projections to the DCN were colabeled with antibodies against VGluT2, a glutamate transporter. Anterogradely labeled endings in the DCN formed asymmetric postsynaptic densities, a feature of excitatory neurotransmission. These descending projections to the DCN from the IC were topographic and suggest a feedback pathway that could underlie a frequency‐specific enhancement of some acoustic signals and suppression of others. The involvement of this IC–DCN circuit is especially noteworthy when considering the gating of ascending signal streams for auditory processing. J. Comp. Neurol. 525:773–793, 2017. © 2016 Wiley Periodicals, Inc.
Amine‐Appended Hierarchical Ca‐A Zeolite for Enhancing CO2/CH4 Selectivity of Mixed‐Matrix Membranes
Authors: Nguyen Tien Hoa , Gong Heqing , Lee Siew Siang , Bae Tae‐Hyun
Published: August 2016

An amine‐appended hierarchical Ca‐A zeolite that can selectively capture CO2 was synthesized and incorporated into inexpensive membrane polymers, in particular polyethylene oxide and Matrimid, to design mixed‐matrix membranes with high CO2/CH4 selectivities. Binary mixture permeation testing reveals that amine‐appended mesoporous Ca‐A is highly effective in improving CO2/CH4 selectivity of polymeric membranes. In particular, the CO2/CH4 selectivity of the polyethylene oxide membrane increases from 15 to 23 by incorporating 20 wt % amine‐appended Ca‐A zeolite. Furthermore, the formation of filler/polymer interfacial defects, which is typically found in glassy polymer‐zeolite pairs, is inhibited owing to the interaction between the amine groups on the external surface of zeolites and polymer chains. Our results suggest that the amine‐appended hierarchial Ca‐A, which was utilized in membrane fabrication for the first time, is a good filler material for fabricating a CO2‐selective mixed‐matrix membrane with defect‐free morphology.
Effective Atom–Molecule Conversions Using Radio Frequency Fields
Authors: Ding Yijue , Pérez‐Ríos Jesús , Greene Chris H.
Published: August 2016

The present study is inspired by the Wieman group experiment [Phys. Rev. Lett. 2005, 95, 190404], in which they use a slow modulated magnetic field to effectively transfer rubidium atoms into cold molecules near a Feshbach resonance. We develop a time‐dependent collision theory based on two channel model potentials to study the atom–molecule population transfer induced by a single‐color radio frequency field in an ultracold 87Rb gas. Wave‐packet dynamical simulations allow an investigation of both bound–bound transitions and free–bound transitions. The effects of temperature, detuning and the RF amplitude on the population transfer are discussed in detail. Some of our simulations suggest that oscillatory atom–molecule conversion could originate from the long coherence time of the wave packet. This coherence time is unusually long in ultracold gases because the collision energy is typically quite well‐defined.
The Impact of Breakthrough Therapy Designation on Development Strategies and Timelines for Nononcology Drugs and Vaccines
Authors: Poirier AF , Murphy WR
Published: August 2016

The US Food and Drug Administration (FDA) Safety and Innovation Act (FDASIA, 2012) introduced the Breakthrough Therapy Designation (BTD), a new tool to expedite development of medicines to treat serious or life‐threatening diseases. The majority of BTDs have gone to oncology drugs, and a recent publication by Shea et al.1 reviewed the impact of BTD on oncology drug development. This article reviews the impact of BTD on development strategies and timelines for nononcology drugs.
Clinical inter‐rater reliability of postural control techniques
Authors: Yuasa Ken , Ihara Yoshiaki , Takei Yoshiko , Groher Michael E. , Takahashi Koji
Published: August 2016

Effectiveness of postural control techniques to compensate for oropharyngeal dysphagia have been recommended and used by several clinicians. However, the inter‐rater reliability of these techniques is not well understood. The purpose of this study was to clarify the ambiguity of postural control techniques using statistical analyses. A total of 50 clinicians involved in dysphagia treatment participated in this study, where a healthy male served as the simulated patient. The following clinically used postures were measured by two investigators on two separate days: chin down, right/left incline, and right/left rotation. Postural angles were measured twice by two investigators on each day. Data obtained for the angle of each posture were visually displayed. Data from both investigators were assessed for each posture using the Youden plot, which analyzes data variability for systematic errors and accidental errors separately. The correlation coefficient for examining the measurement error between investigators was calculated. The results showed considerable variation between clinicians regarding the postures used, and significant differences were noted each day. The correlation coefficient for a total of four measurements was more often lower on Day 2 than that on Day 1. The details of the instructions provided by clinicians were not fixed, and the same specified posture was not reproduced even when instructions were provided to the same subject. These findings suggest poor inter‐rater reliability because of the variability of selected postures when using statistical analyses. Therefore, standardized postures need to be developed that can be easily measured and reproduced.
Association between periodontal condition and kidney dysfunction in Japanese adults: A cross‐sectional study
Authors: Naruishi Koji , Oishi Keiji , Inagaki Yuji , Horibe Masumi , Bando Mika , Ninomiya Masami , Kawahara Kazuhiko , Minakuchi Jun , Kawashima Shu , Shima Kenji , Kido Jun‐ichi , Nagata Toshihiko
Published: August 2016

Recent studies have demonstrated that chronic kidney disease (CKD) may be associated with the progression of periodontal disease. Diabetes mellitus (DM) is a major risk factor for CKD. The objective of this study was to clarify the relationship between periodontal condition and kidney dysfunction in patients who had kidney failure with or without DM. One hundred sixty‐four patients with kidney dysfunction were enrolled (male: N = 105; female: N = 59), and the relationship between periodontal condition and kidney dysfunction was analyzed in a cross‐sectional study. The subjects were divided into three groups: (a) patients with DM, (b) dialysis patients with nephropathy due to various kidney diseases, and (c) dialysis patient with nephropathy due to DM (diabetic nephropathy). Then, the effect of DM on the periodontal condition was analyzed. The patients were also stratified by CKD stage (into G1–G5) using the estimated glomerular filtration rate (eGFR), and the G5 group was divided in patients with or without DM. Correlations between eGFR and parameters of periodontal condition were calculated in patients from G1 to G4. The number of missing teeth was significantly higher in dialysis patients with diabetic nephropathy than in patients with DM, whereas alveolar bone loss did not show a significant difference among the three groups. In addition, the G5 patients with DM had a significantly higher number of missing teeth than the other CKD groups, whereas alveolar bone loss did not show a significant difference. In G5 patients with DM, Community Periodontal Index and Oral Hygiene Index scores were significantly higher than in G1‐4 patients with DM. There was a significant negative correlation between eGFR and the number of missing teeth. Patients with diabetic nephropathy have a higher rate of periodontal problems such as missing teeth in Japanese adults.
High‐Performance Carbon Aerogel Air Cathodes for Microbial Fuel Cells
Authors: Zhang Xiaoyuan , He Weihua , Zhang Rufan , Wang Qiuying , Liang Peng , Huang Xia , Logan Bruce E. , Fellinger Tim‐Patrick
Published: August 2016

Microbial fuel cells (MFCs) can generate electricity from the oxidation of organic substrates using anodic exoelectrogenic bacteria and have great potential for harvesting electric energy from wastewater. Improving oxygen reduction reaction (ORR) performance at a neutral pH is needed for efficient energy production. Here we show a nitrogen doped (≈4 wt%) ionothermal carbon aerogel (NDC) with a high surface area, large pore volume, and hierarchical porosity, with good electrocatalytic properties for ORR in MFCs. The MFCs using NDC air cathodes achieved a high maximum power density of 2300 mW m−2, which was 1.7 times higher than the most commonly used Pt/C air cathodes and also higher than most state‐of‐the‐art ORR catalyst air cathodes. Rotating disk electrode measurements verified the superior electrocatalytic activity of NDC with an efficient four‐electron transfer pathway (n=3.9). These findings highlight NDC as a better‐performing and cost‐efficient catalyst compared with Pt/C, making it highly viable for MFC applications.
Engineering of Sub‐Nanometer SiOx Thickness in Si Photocathodes for Optimized Open Circuit Potential
Authors: Das Chittaranjan , Kot Malgorzata , Henkel Karsten , Schmeisser Dieter
Published: August 2016

Silicon is one of the most promising materials to be used for tandem‐cell water‐splitting devices. However, the electrochemical instability of bare Si makes it difficult to be used for stable devices. Besides that, the photovoltage loss in Si, caused by several factors (e.g., metal oxide protection layer and/or SiO2/Si or catalyst/Si interface), limits its use in these devices. In this work, we present that an optimized open circuit potential (OCP) of Si can be obtained by controlling the SiOx thickness in sub‐nanometer range. It can be done by means of a simple and cost‐effective way using the combination of a wet chemical etching and the low temperature atomic layer deposition (ALD) of TiO2. We have found that a certain thickness of the native SiOx is necessary to prevent further oxidation of the Si photocathode during the ALD growth of TiO2. Moreover, covering the Si photocathode with an ALD TiO2 layer enhances its stability.
Protective Effect of Metformin against Acute Inflammation and Oxidative Stress in Rat
Authors: Pandey Abhimanu , Kumar Vijay L.
Published: August 2016

Preclinical Research

The antidiabetic drug, metformin, can inhibit the release of inflammatory mediators in several disease conditions. The present study was carried out to evaluate the efficacy of metformin in ameliorating edema formation, oxidative stress, mediator release and vascular changes associated with acute inflammation in the rat carrageenan model. Metformin dose‐dependently inhibited paw swelling induced by carrageenan and normalized the tissue levels of the inflammatory markers myeloperoxidase and nitrite. It also maintained oxidative homeostasis as indicated by near normal levels of the oxidative stress markers glutathione, thiobarbituric acid reactive substances, catalase and superoxide dismutase. The histopathology of the paw tissue in metformin‐treated animals was similar to that in normal paw and had similar effects to diclofenac. In a rat peritonitis model, metformin reduced vascular permeability and cellular infiltration. In conclusion, this study shows that metformin has a potential for use in treating various inflammatory conditions.
Modulation of growth cone filopodial length by carbon monoxide
Authors: Estes Stephen , Artinian Liana , Rehder Vincent
Published: August 2016

Carbon monoxide (CO) is physiologically produced via heme degradation by heme oxygenase enzymes. Whereas CO has been identified as an important physiological signaling molecule, the roles it plays in neuronal development and regeneration are poorly understood. During these events, growth cones guide axons through a rich cellular environment to locate target cells and establish synaptic connections. Previously, we have shown that another gaseous signaling molecule, nitric oxide (NO), has potent effects on growth cone motility. With NO and CO sharing similar cellular targets, we wanted to determine whether CO affected growth cone motility as well. We assessed how CO affected growth cone filopodial length and determined the signaling pathway by which this effect was mediated. Using two well‐characterized neurons from the freshwater snail, Helisoma trivolvis, it was found that the CO donor, carbon monoxide releasing molecule‐2 (CORM‐2), increased filopodial length. CO utilized a signaling pathway that involved the activation of soluble guanylyl cyclase, protein kinase G, and ryanodine receptors. While increases in filopodial length often occur from robust increases in intracellular calcium levels, the timing in which CO increased filopodial length corresponded with low basal calcium levels in growth cones. Taken together with findings of a heme oxygenase‐like protein in the Helisoma nervous system, these results provide evidence for CO as a modulator of growth cone motility and implicate CO as a neuromodulatory signal during neuronal development and/or regeneration. © 2016 Wiley Periodicals, Inc. Develop Neurobiol 77: 677–690, 2017
Eleven years of crop diversification alters decomposition dynamics of litter mixtures incubated with soil
Authors: McDaniel M. D. , Grandy A. S. , Tiemann L. K. , Weintraub M. N.
Published: August 2016

Agricultural crop rotations have been shown to increase soil carbon (C), nitrogen (N), and microbial biomass. The mechanisms behind these increases remain unclear, but may be linked to the diversity of crop residue inputs to soil organic matter (SOM). We used a residue mixture incubation to examine how variation in long‐term diversity of plant communities in agroecosystems influences decomposition of residue mixtures, thus providing a comparison of the effects of plant diversification on decomposition in the long term (via crop rotation) and short term (via residue mixtures). Three crop residue mixtures, ranging in diversity from two to four species, were incubated for 360 d with soils from five crop rotations, ranging from monoculture corn (mC) to a complex five‐crop rotation. In response, we measured fundamental soil pools and processes underlying C and N cycling. These included soil respiration, inorganic N, microbial biomass, and extracellular enzymes. We hypothesized that soils with more diverse cropping histories would show greater synergistic mixture effects than mC. For most variables (except extracellular enzymes), crop rotation history, or the long‐term history of plant diversity in the field, had a stronger effect on soil processes than mixture composition. In contrast to our hypothesis, the mC soil had nearly three and seven times greater synergistic mixture effects for respiration and microbial biomass N, respectively, compared with soils from crop rotations. This was due to the low response of the mC soils to poor quality residues (corn and wheat), likely resulting from a lack of available C and nutrients to cometabolize these residues. These results indicate that diversifying crop rotations in agricultural systems alter the decomposition dynamics of new residue inputs, which may be linked to the benefits of increasing crop rotation diversity on soil nutrient cycling, SOM dynamics, and yields.
Spatiotemporal expression of endogenous TLR4 ligands leads to inflammation and bone erosion in mouse collagen‐induced arthritis
Authors: Kiyeko Gaëlle Wambiekele , Hatterer Eric , Herren Suzanne , Di Ceglie Irene , van Lent Peter L. , Reith Walter , Kosco‐Vilbois Marie , Ferlin Walter , Shang Limin
Published: August 2016

Increased expression of endogenous Toll‐like receptor 4 (TLR4) ligands (e.g., Tenascin‐C, S100A8/A9, citrullinated fibrinogen (cFb) immune complexes) has been observed in patients with rheumatoid arthritis (RA). However, their roles in RA pathogenesis are not well understood. Here, we investigated the expression kinetics and role of endogenous TLR4 ligands in the murine model of collagen‐induced arthritis (CIA). Tenascin‐C was upregulated in blood early in CIA, and correlated positively with the clinical score at day 56. Levels of S100A8/A9 increased starting from day 28, peaking at day 42, and correlated positively with joint inflammation. Levels of anti‐cFb antibodies increased during the late phase of CIA and correlated positively with both joint inflammation and cartilage damage. Blockade of TLR4 activation at the time of the first TLR4 ligand upregulation prevented clinical and histological signs of arthritis. A TLR4‐dependent role was also observed for Tenascin‐C and cFb immune complexes in osteoclast differentiation in vitro. Taken together, our data suggests that the pathogenic contribution of TLR4 in promoting joint inflammation and bone erosion during CIA occurs via various TLR4 ligands arising at different stages of disease. The data also suggests that Blockade of TLR4 with monoclonal antibodies is a promising strategy in RA treatment.
Prolonging the Emissive Lifetimes of Copper(I) Complexes with 3MLCT and 3(π–π*) State Equilibria – A Fluorene Moiety as an “Energy Reservoir”
Authors: Yi Cheng , Xu Shengxian , Wang Jinglan , Zhao Feng , Xia Hongying , Wang Yibo
Published: August 2016

Two CuI complexes, [Cu(imPhen)(POP)]PF6 (1, imPhen = 1H‐imidazo[4,5‐f][1,10]phenanthroline, POP = bis[2‐diphenylphosphino]phenyl ether) and [Cu(Flu‐imPhen)(POP)]PF6 {2, Flu‐imPhen = 2‐(9H‐fluoren‐2‐yl)‐1H‐imidazo[4,5‐f][1,10]phenanthroline} were synthesized and characterized. a weak metal‐to‐ligand charge‐transfer (MLCT) absorption band at λ = 401 nm with a relatively low molar extinction coefficient (ε = 3170 m–1 cm–1) was observed for 1. In contrast, 2 displayed a higher MLCT absorption band at λ = 405 nm (ε = 5400 m–1 cm–1) owing to the incorporation of a fluorene group to imPhen ring. Complexes 1 and 2 exhibited similar emission wavelengths and quantum yields (λem = 564 nm, ϕ = 11.2 % for 1 and λem = 568 nm, ϕ = 9.0 % for 2); however, the excited‐state lifetime of 2 (τ = 51.2 µs) was almost four times longer than that of 1 (τ = 13.8 µs). The prolonged luminescence lifetime of 2 was rationalized by the reversible energy transfer between the 3MLCT state of the Cu atom and the 3π→π* state of fluorene moiety. To the best of our knowledge, this is the first use of a fluorene group as a triplet energy reservoir to extend the excited‐state lifetime of an emissive 3MLCT state of a CuI complex.
Tellurites of Hexavalent Uranium: First Observation of Polymerized (UO4)2– Tetraoxido Cores
Authors: Zadoya Anastasiya I. , Siidra Oleg I. , Bubnova Rimma S. , Nazarchuk Evgeny V. , Bocharov Sergey N.
Published: August 2016

Two novel Ca2(UO3)(TeO3)2 (1) and K2(UO2)2O2(TeO3) (2) uranyl tellurites were obtained from telluric acid, used as a starting reagent for both compounds. In 1, the tetraoxido core is coordinated by TeO3 groups and UO4 squares polymerize into [UO3] chains. The tetraoxido core coordination modes in compound 1 are unique. New layered ⋡2[(UO2)2(TeO3)O2]2– topology is observed for 2. Both of the compounds were studied by the means of high‐temperature X‐ray diffraction. The thermal decomposition of 1 and 2 is different and leads to formation of uranate compounds.
Superparamagnetic Core–Shell Metal–Organic Framework Fe3O4/Cu3(btc)2 Microspheres and Their Catalytic Activity in the Aerobic Oxidation of Alcohols and Olefins
Authors: Li Jie , Gao Hongyi , Tan Li , Luan Yi , Yang Mu
Published: August 2016

Core–shell structured Fe3O4/Cu3(btc)2 (btc = 1,3,5‐benzenetricarboxylate) microspheres have been successfully synthesized by coating the metal–organic frameworks on poly(acrylic acid) (PAA) functionalized Fe3O4 microspheres by the layer‐by‐layer assembly method. The MOF composite exhibited excellent catalytic activity in the aerobic oxidation of alcohols and the epoxidation of olefins due to the porosity of MOFs and large amount of readily accessible Cu2+. Furthermore, the catalyst could be easily segregated from the catalytic system by using an external magnetic field due to its magnetic properties. The heterogeneous catalyst displayed good reusability and broad reagent scope in the aerobic oxidation of alcohols and epoxidation of olefins.
Reactivity of an NHC‐Stabilized Silylene towards Lewis Acids and Lewis Bases
Authors: Cui Haiyan , Wu Meng , Teng Peng
Published: August 2016

The reactivity of N‐heterocyclic carbene stabilized (NHC‐stabilized) aminochlorosilylene ArN(SiMe3)Si(IiPr)Cl (1, Ar = 2,6‐iPr2C6H3, IiPr = 1,3‐diisopropyl‐4,5‐dimethylimidazol‐2‐ylidene) with selected Lewis acids and Lewis bases is described. Treatment of 1 with BH3·THF yielded 1·BH3 (2) quantitatively. Compound 2 is a rare example of an air‐insensitive silylene–borane adduct showing both acidic and basic properties of chlorosilylene in a single molecule. Crystals of 1–(CH2)3CH2OB(C6F5)3 (3) were obtained from the reaction of 1 with B(C6F5)3 in THF. For the first time, a frustrated Lewis pair (FLP) composed of a silylene and a substituted borane was observed to activate small molecules. Reaction of 1 with IMe4 (IMe4 = 1,3,4,5‐tetramethylimidazol‐2‐ylidene) at room temperature afforded silylene ArN(SiMe3)Si(IMe4)Cl (4), which represents a rare example of an NHC‐stabilized silylene synthesized through ligand exchange.
Preparation, Characterization, Redox, and Photoinduced Electron‐Transfer Properties of the NIR‐Absorbing N‐Ferrocenyl‐2‐pyridone BODIPYs
Authors: Zatsikha Yuriy V. , Didukh Natalia O. , Blesener Tanner , Kayser Mathew P. , Kovtun Yuriy P. , Blank David A. , Nemykin Victor N.
Published: August 2016

Mono‐ and di‐(N‐ferrocenyl‐2‐pyridone)‐containing BODIPYs were prepared using a set of ferrocene‐enamine cyclization reactions. The target compounds were characterized by UV‐Vis, NMR, and mass spectrometry, while their redox properties were probed by the electrochemical, spectroelectrochemical, and chemical oxidation methods. Redox properties of the di‐(ferrocenyl)‐containing BODIPY are suggestive of a lack of electronic coupling between the two ferrocene groups. Oxidation of the ferrocene(s) in the target BODIPYs results in their observable fluorescence, while transient absorption spectroscopy data indicate fast electron‐transfer from ferrocene donor to the photoexcited BODIPY acceptor. Density functional theory (DFT) and time‐dependent DFT (TDDFT) methods were used to elucidate electronic structures of the organometallic BODIPYs and confirm the presence of the low‐energy metal‐to‐ligand charge‐transfer states in the NIR region.
The Diphosphorus Complex [Cp2Mo2(CO)4(η2‐P2)] as a Building Block for the Synthesis of Mixed‐Hybrid Coordination Polymers
Authors: Moussa Mehdi Elsayed , Attenberger Bianca , Fleischmann Martin , Schreiner Andrea , Scheer Manfred
Published: August 2016

The three‐component reaction of the tetrahedral diphosphorus complex [Cp2Mo2(CO)4(η2‐P2)] (1), with Ag[BF4] (2) in the presence of 2,2′‐bipyrimidine (3) leads to the formation of the two novel two‐dimensional networks 4 and 5. Compound 4 is a new two‐dimensional organometallic‐organic hybrid polymer, while derivative 5 represents a unique two‐dimensional organometallic‐inorganic‐organic hybrid polymer. These results show the possibility of synthesizing a new class of coordination polymers, which could not be obtained from two‐component reactions with organic molecules in addition of metal ions.
Transition‐Metal Carbonyl Complexes and Electron‐Donating Properties of N‐Heterocyclic‐Carbene–Phosphinidene Adducts
Authors: Bockfeld Dirk , Doddi Adinarayana , Jones Peter G. , Tamm Matthias
Published: August 2016

Invited for the cover of this issue is the group of Matthias Tamm from the Technische Universität Braunschweig, Germany. The cover image shows the structure of an N‐heterocyclic‐carbene–phosphinidene–tungsten complex, which was used to establish that NHC–phosphinidenes represent a new class of strongly electron‐donating phosphorus ligands.
Stabilized Sulfur Ylide Mediated Cyclopropanations and Formal [4+1] Cycloadditions of 3‐Acyl‐2H‐chromenones and Their Imines
Authors: Meng Xiang‐Suo , Jiang Shan , Xu Xiao‐Yun , Wu Qiang‐Xian , Gu Yu‐Cheng , Shi De‐Qing
Published: August 2016

Stabilized sulfur ylide mediated cyclopropanation and formal [4+1] cycloaddition of 3‐acyl‐2H‐chromenones and their imines were explored. The transformations could be performed under mild conditions and were shown to have wide substrate scopes and significant functional‐group tolerance; furthermore, the reactions proceeded with excellent regioselectivity. Thus, they are powerful methods for the one‐pot synthesis of highly functionalized cyclopropane‐ and dihydropyrrole‐fused chromen‐2‐one derivatives.
Highly Efficient One‐Step Synthesis of N‐Trimethylsiloxy Alkyl Imidothioates
Authors: Kuciński Krzysztof , Hreczycho Grzegorz
Published: August 2016

A hitherto unknown synthetic pathway for the synthesis of N‐trimethylsiloxy alkyl imidothioates has been presented. The catalyst‐free route uses a range of aromatic, aliphatic, and heterocyclic thiols in the presence of nitroalkanes and hexamethyldisilazane (HMDS). This unusual method expands upon the knowledge of nitro compounds and demonstrates their importance not only as solvents but also as valuable organic reagents. This reaction proceeds under mild conditions and is characterized by excellent yields and a facile workup.
Seismic risk assessment considering cumulative damage due to aftershocks
Authors: Jalayer Fatemeh , Ebrahimian Hossein
Published: August 2016

Calculating the limit state (LS) exceedance probability for a structure considering the main seismic event and the triggered aftershocks (AS) is complicated both by the time‐dependent rate of aftershock occurrence and also by the cumulative damage caused by the sequence of events. Taking advantage of a methodology developed previously by the authors for post‐mainshock (MS) risk assessment, the LS probability due to a sequence of mainshock and the triggered aftershocks is calculated for a given aftershock forecasting time window. The proposed formulation takes into account both the time‐dependent rate of aftershock occurrence and also the damage accumulation due to the triggered aftershocks. It is demonstrated that an existing reinforced concrete moment‐resisting frame with infills subjected to the main event and the triggered sequence exceeds the near‐collapse LS. On the other hand, the structure does not reach the onset of near‐collapse LS when the effect of triggered aftershocks is not considered. It is shown, based on simplifying assumptions, that the derived formulation yields asymptotically to the same Poisson‐type functional form used when the cumulative damage is not being considered. This leads to a range of approximate solutions by substituting the fragilities calculated for intact, MS‐damaged, and MS‐plus‐one‐AS‐damaged structures in the asymptotic simplified formulation. The latter two approximate solutions provide good agreement with the derived formulation. Even when the fragility of intact structure is employed, the approximate solution (considering only the time‐dependent rate of aftershock occurrence) leads to higher risk estimates compared with those obtained based on only the mainshock. Copyright © 2016 John Wiley & Sons, Ltd.
Functional dissociation between anterior temporal lobe and inferior frontal gyrus in the processing of dynamic body expressions: Insights from behavioral variant frontotemporal dementia
Authors: Jastorff Jan , De Winter Francois‐Laurent , Van den Stock Jan , Vandenberghe Rik , Giese Martin A. , Vandenbulcke Mathieu
Published: August 2016

Several brain regions are involved in the processing of emotional stimuli, however, the contribution of specific regions to emotion perception is still under debate. To investigate this issue, we combined behavioral testing, structural and resting state imaging in patients diagnosed with behavioral variant frontotemporal dementia (bvFTD) and age matched controls, with task‐based functional imaging in young, healthy volunteers. As expected, bvFTD patients were impaired in emotion detection as well as emotion categorization tasks, testing dynamic emotional body expressions as stimuli. Interestingly, their performance in the two tasks correlated with gray matter volume in two distinct brain regions, the left anterior temporal lobe for emotion detection and the left inferior frontal gyrus (IFG) for emotion categorization. Confirming this observation, multivoxel pattern analysis in healthy volunteers demonstrated that both ROIs contained information for emotion detection, but that emotion categorization was only possible from the pattern in the IFG. Furthermore, functional connectivity analysis showed reduced connectivity between the two regions in bvFTD patients. Our results illustrate that the mentalizing network and the action observation network perform distinct tasks during emotion processing. In bvFTD, communication between the networks is reduced, indicating one possible cause underlying the behavioral symptoms. Hum Brain Mapp 37:4472–4486, 2016. © 2016 Wiley Periodicals, Inc.
Multimodal MRI reveals structural connectivity differences in 22q11 deletion syndrome related to impaired spatial working memory
Authors: O'Hanlon Erik , Howley Sarah , Prasad Sarah , McGrath Jane , Leemans Alexander , McDonald Colm , Garavan Hugh , Murphy Kieran C
Published: August 2016

Introduction

Impaired spatial working memory is a core cognitive deficit observed in people with 22q11 Deletion syndrome (22q11DS) and has been suggested as a candidate endophenotype for schizophrenia. However, to date, the neuroanatomical mechanisms describing its structural and functional underpinnings in 22q11DS remain unclear. We quantitatively investigate the cognitive processes and associated neuroanatomy of spatial working memory in people with 22q11DS compared to matched controls. We examine whether there are significant between‐group differences in spatial working memory using task related fMRI, Voxel based morphometry and white matter fiber tractography.

Materials and Methods

Multimodal magnetic resonance imaging employing functional, diffusion and volumetric techniques were used to quantitatively assess the cognitive and neuroanatomical features of spatial working memory processes in 22q11DS. Twenty‐six participants with genetically confirmed 22q11DS aged between 9 and 52 years and 26 controls aged between 8 and 46 years, matched for age, gender, and handedness were recruited.

Results

People with 22q11DS have significant differences in spatial working memory functioning accompanied by a gray matter volume reduction in the right precuneus. Gray matter volume was significantly correlated with task performance scores in these areas. Tractography revealed extensive differences along fibers between task‐related cortical activations with pronounced differences localized to interhemispheric commissural fibers within the parietal section of the corpus callosum.

Conclusions

Abnormal spatial working memory in 22q11DS is associated with aberrant functional activity in conjunction with gray and white matter structural abnormalities. These anomalies in discrete brain regions may increase susceptibility to the development of psychiatric disorders such as schizophrenia. Hum Brain Mapp 37:4689–4705, 2016. © 2016 Wiley Periodicals, Inc.
A Stated Preference Approach to Assess whether Health Status Impacts on Marginal Utility of Consumption
Authors: Gyrd‐Hansen Dorte
Published: August 2016

A sample of Danish citizens (n = 2000) was asked to participate in a hypothetical experiment in which they could self‐insure against a certain loss in income across two periods of time (one in which the person is in good health and one in which the person is in poorer health). Our results suggest that reduced health impacts on the marginal utility of consumption, but not in a linear fashion. Amongst a majority of respondents inferior, health increases the marginal utility of consumption for intermediate health states, whereas this is not the case for less and more severe health states. Copyright © 2016 John Wiley & Sons, Ltd.
New strategies in myelofibrosis: the evolving paradigm of disease pathogenesis, prognostication and treatment
Authors: Palandri Francesca , Auteri Giuseppe , Baccarani Michele
Published: August 2016

Myelofibrosis (MF) is the most severe among the classical Philadelphia‐negative myeloproliferative neoplasms that also include essential thrombocytemia and polycythemia vera. Myelofibrosis is characterized by numerous genetic lesions, often variously associated with each other, and by an aggressive clinical phenotype leading to severely reduced survival. Also, the inflammatory microenvironment plays a key role in disease initiation and progression. Because of the complexity of its pathogenesis and the variability of clinical features, MF is a disease that requires a personalized approach and remains orphan of curative treatments besides allogeneic transplantation. JAK2 inhibitors have marked a remarkable progress, because they alleviate systemic symptoms and reduce splenomegaly but have a limited effect on survival, on mutation load, and on marrow fibrosis. Here, we review the main contributing factors to MF pathogenesis and prognosis, focusing on how these factors relate to therapeutic choices. We discuss results from ongoing studies of JAK2 inhibitors and report on new therapeutic strategies that proved effective in early preclinical and clinical trials, including combination treatments, antifibrotic agents, and telomerase inhibitors.