bluuebunny/crossref_metadata_2025 huggingface dataset:
Comprehensive Understanding of the Role of Brønsted and Lewis Acid Sites in Glucose Conversion into 5‐Hydromethylfurfural
Authors: Li Xiangcheng , Peng Kaihao , Liu Xiaohui , Xia Qineng , Wang Yanqin
Published: November 2016

The conversion of glucose and selectivity into 5‐hydromethylfurfural (HMF) were investigated over various silica–alumina composite (AlSiO) catalysts. The type, amount, and strength of the acidic sites were characterized by using NH3 temperature‐programmed desorption and FTIR spectroscopy and then correlated to the catalytic conversion of glucose into HMF to provide a quantitative relationship between the acidity and product selectivity. Lewis acid sites played an important role in glucose conversion, which can enhance the isomerization of glucose to fructose, whereas Brønsted acid sites had a detrimental effect. HMF selectivity had an almost linear relationship with the weak/total Lewis acid ratio (L*/L), indicating that weak Lewis acids could promote formation of HMF. The medium‐to‐strong Lewis acid sites can enhance the formation of undesired byproducts (levulinic acid, humins). The Brønsted to Lewis acid ratio (B/L) had an influence on the HMF selectivity; at similar L*/L ratios, volcano curves were obtained with the increase of the B/L ratio, but the influence was not as great as that of the L*/L ratio. Nb‐doped AlSiO catalysts were prepared and used in the conversion of glucose into HMF, which also confirmed the above findings. Under the optimized conditions, the HMF selectivity can reach 71 % at 92.6 % conversion of glucose with no clear decline after four catalytic cycles.
Towards Understanding Structure–Activity Relationships of Ni–Mo–W Sulfide Hydrotreating Catalysts
Authors: Hein Jennifer , Gutiérrez Oliver Y. , Albersberger Sylvia , Han Jinyi , Jentys Andreas , Lercher Johannes A.
Published: November 2016

The relation between activity and selectivity of a series of unsupported Ni–Mo, Ni–W, and Ni–Mo–W sulfides and the physicochemical properties of the sulfides and oxide precursors were explored. Bimetallic oxide precursors were a crystalline molybdate with layered structure ((NH4)HNi2(OH)2(MoO4)2) or a wolframite‐type nickel tungstate (NiWO4). Trimetallic precursors were mixed Mo–W–Ni phases appearing amorphous in XRD analysis, in which metal cations had environments similar to those in the bimetallic precursors. The XRD‐amorphous layered structure (obtained for a Ni–Mo–W precursor) led to the fastest sulfidation of Ni cations. The proximity of metal cations in precursors was retained after sulfidation, which lead to intralayer mixed Mo1−xWxS2 (in trimetallic materials) and varying concentrations of Ni at the perimeter of the Mo(W)S2 slabs. At MoS2 and WS2 edges, Ni has a square‐pyramidal coordination, which is significantly distorted at the Mo–W mixed edges. The catalyst with the lowest Mo/W–Ni coordination had the lowest rates for hydrodenitrogenation of o‐propylaniline and hydrodesulfurization of dibenzothiophene. Among the materials with significant Ni–Mo(W) coordinations, the most active sulfide catalyst at low temperatures was Ni–W with highly defective slabs, at high temperatures the Ni–Mo–W sulfide with the highest Ni concentration at the perimeter was the most active catalyst.
Hydrogen and Chemicals from Renewable Alcohols by Organometallic Electroreforming
Authors: Bellini Marco , Filippi Jonathan , Miller Hamish A. , Oberhauser Werner , Vizza Francesco , He Qinggang , Grützmacher Hansjorg
Published: November 2016

The selective and simultaneous production of hydrogen and chemicals from renewable alcohols was accomplished by using an electrolyzer, for which the anode electrocatalyst was an organometallic complex, [Rh(OTf)(trop2NH){P(4‐BuC6H4)3}] (trop2NH=bis(5H‐dibenzo[a,d]cyclohepten‐5‐yl)amine; −OTf=CF3SO3−), deposited on amorphous carbon and appropriately designed to promote the partial and selective oxidation of alcohols. The electrolyzer converted alcohols into industrially relevant chemicals and high‐purity hydrogen at high volume and with very low energy consumption.
9,10‐Diaminoanthracenes Revisited: The Influence of N‐Substituents on Their Electronic States
Authors: Uebe Masashi , Kato Tatsuhisa , Tanaka Kazuyoshi , Ito Akihiro
Published: November 2016

The electronic and molecular structures of 9,10‐diamino‐substituted anthracenes with different N‐substituents have been re‐examined. In particular, different N‐substituents influence both the electronic and molecular structures of the oxidized species of 9,10‐diaminoanthracenes. The anthrylene moiety of 9,10‐bis(N,N‐di(p‐anisyl)amino)anthracene retains its planarity during the course of two successive one‐electron oxidations, whereas 9,10‐bis(N,N‐dimethylamino)anthracene and 9,10‐bis(N‐p‐anisyl‐N‐methylamino)anthracene undergo a substantial structural change to a butterfly‐like structure through a two‐electron oxidation process. The structural changes observed for the oxidized states are ascribed to significant differences in the frontier molecular orbitals of the above‐mentioned three kinds of 9,10‐diaminoanthracenes due to different extents of mixing between the amine‐localized and anthrylene‐localized orbitals.
Alkyne Addition and Insertion Reactions of [(Me3Si)3Si]2Ge⋅PMe3
Authors: Walewska Małgorzata , Baumgartner Judith , Marschner Christoph , Albers Lena , Müller Thomas
Published: November 2016

Silylated germylene–PMe3 adducts exchange their phosphane moiety smoothly for an N‐heterocyclic carbene or isocyanide species to form their respective base adducts. Reaction of the silylated germylene–PMe3 adducts with monosubstituted alkynes produce germylene adducts with the alkyne inserted into a Ge−Si bond. A computational study of this process provides evidence for the initial formation of a germirene, which rearranges to a vinylgermylene species. The thermodynamic driving force for this reaction is provided by subsequent adduct formation with PMe3. Reaction of the PMe3 adduct of bis[(trimethylsilyl)silyl]germylene with disubstituted alkynes leads to the formation of stable germirenes, which can be isomerized further to silagermetes.
Identification of Compounds that Selectively Stabilize Specific G‐Quadruplex Structures by Using a Thioflavin T‐Displacement Assay as a Tool
Authors: Jamroskovic Jan , Livendahl Madeleine , Eriksson Jonas , Chorell Erik , Sabouri Nasim
Published: November 2016

Small molecules are used in the G‐quadruplex (G4) research field in vivo and in vitro, and there are increasing demands for ligands that selectively stabilize different G4 structures. Thioflavin T (ThT) emits an enhanced fluorescence signal when binding to G4 structures. Herein, we show that ThT can be competitively displaced by the binding of small molecules to G4 structures and develop a ThT‐displacement high‐throughput screening assay to find novel and selective G4‐binding compounds. We screened approximately 28 000 compounds by using three different G4 structures and identified eight novel G4 binders. Analysis of the structural conformation and stability of the G4 structures in presence of these compounds demonstrated that the four compounds enhance the thermal stabilization of the structures without affecting their structural conformation. In addition, all four compounds also increased the G4‐structure block of DNA synthesis by Taq DNA polymerase. Also, two of these compounds showed selectivity between certain Schizosaccharomyces pombe G4 structures, thus suggesting that these compounds or their analogues can be used as selective tools for G4 DNA studies.
Stereoelectronic Chameleons: The Donor–Acceptor Dichotomy of Functional Groups
Authors: Vatsadze Sergey Z. , Loginova Yulia D. , dos Passos Gomes Gabriel , Alabugin Igor V.
Published: November 2016

Stereoelectronic factors account for the apparent reversal of donor–acceptor properties of a variety of functional groups by a simple change of their orientation in space. The new reactivity patterns that arise from spatial anisotropy are associated with chameleonic behavior of common organic functionalities.
Structure–Property Relationships in Click‐Derived Donor–Triazole–Acceptor Materials
Authors: Kautny Paul , Bader Dorian , Stöger Berthold , Reider Georg A. , Fröhlich Johannes , Lumpi Daniel
Published: November 2016

To shed light on intramolecular charge‐transfer phenomena in 1,2,3‐triazole‐linked materials, a series of 1,2,3‐triazole‐linked push–pull chromophores were prepared and studied experimentally and computationally. Investigated modifications include variation of donor and/or acceptor strength and linker moiety as well as regioisomers. Photophysical characterization of intramolecular charge‐transfer features revealed ambipolar behavior of the triazole linker, depending on the substitution position. Furthermore, non‐centrosymmetric materials were subjected to second‐harmonic generation measurements, which revealed the high nonlinear optical activity of this class of materials.
Layered Post‐Transition‐Metal Dichalcogenides (X−M−M−X) and Their Properties
Authors: Luxa Jan , Wang Yong , Sofer Zdenek , Pumera Martin
Published: November 2016

AIIIBVI chalcogenides are an interesting group of layered semiconductors with several attractive properties, such as tunable band gaps and the formation of solid solutions. Unlike the typically sandwiched structure of transition‐metal dichalcogenides, AIIIBVI layered chalcogenides with hexagonal symmetry are stacked through the X−M−M−X motif, in which M is gallium and indium, and X is sulfur, selenium, and tellurium. In view of the inadequate study of the electrochemical properties and great interest in layered materials towards energy‐related research, herein the inherent electrochemistry of GaS, GaSe, GaTe, and InSe has been studied, as well as the exploration of their potential as hydrogen evolution reaction (HER) electrocatalysts. All four materials show redox peaks during cyclic voltammetry measurements. Furthermore, insights into catalysis of the HER are provided; these indicate the conductivity and number of active sites of the materials. All of these findings have important implications on their possible applications.
Boroquinol Complexes with Fused Extended Aromatic Backbones: Synthesis and Optical Properties
Authors: Elbert Sven M. , Wagner Philippe , Kanagasundaram Thines , Rominger Frank , Mastalerz Michael
Published: November 2016

Boron‐based dyes are attractive synthetic targets due to their large variability of absorption and emission wavelengths. Through Pictet–Spengler cyclizations, followed by oxidation, π‐extended boroquinols have been synthesized. During optimization of the reaction conditions, an unusual dearylation has been found and mechanistically investigated. For two of the synthesized boroquinols, mechanochromic effects with bathochromic shifts up to 50 nm were found upon grinding.
The First Casbane Hydroperoxides EBC‐304 and EBC‐320 from the Australian Rainforest
Authors: Maslovskaya Lidiya A. , Savchenko Andrei I. , Gordon Victoria A. , Reddell Paul W. , Pierce Carly J. , Parsons Peter G. , Williams Craig M.
Published: November 2016

Investigation of the Australian rainforest plant Croton insularis led to isolation of the first casbane hydroperoxide diterpenes EBC‐304 and EBC‐320. Extensive DFT and electronic circular dichroism (ECD) calculations in combination with 2D NMR spectroscopy determined the absolute configurations. EBC‐304 and EBC‐320 both display significant cytotoxicity.
An Iridium(III) Complex as a Photoactivatable Tool for Oxidation of Amyloidogenic Peptides with Subsequent Modulation of Peptide Aggregation
Authors: Kang Juhye , Lee Shin Jung C. , Nam Jung Seung , Lee Hyuck Jin , Kang Myeong‐Gyun , Korshavn Kyle J. , Kim Hyun‐Tak , Cho Jaeheung , Ramamoorthy Ayyalusamy , Rhee Hyun‐Woo , Kwon Tae‐Hyuk , Lim Mi Hee
Published: November 2016

Aggregates of amyloidogenic peptides are involved in the pathogenesis of several degenerative disorders. Herein, an iridium(III) complex, Ir‐1, is reported as a chemical tool for oxidizing amyloidogenic peptides upon photoactivation and subsequently modulating their aggregation pathways. Ir‐1 was rationally designed based on multiple characteristics, including 1) photoproperties leading to excitation by low‐energy radiation; 2) generation of reactive oxygen species responsible for peptide oxidation upon photoactivation under mild conditions; and 3) relatively easy incorporation of a ligand on the IrIII center for specific interactions with amyloidogenic peptides. Biochemical and biophysical investigations illuminate that the oxidation of representative amyloidogenic peptides (i.e., amyloid‐β, α‐synuclein, and human islet amyloid polypeptide) is promoted by light‐activated Ir‐1, which alters the conformations and aggregation pathways of the peptides. Additionally, their potential oxidation sites are identified as methionine, histidine, or tyrosine residues. Overall, our studies on Ir‐1 demonstrate the feasibility of devising metal complexes as chemical tools suitable for elucidating the nature of amyloidogenic peptides at the molecular level, as well as controlling their aggregation.
Readily Accessible and Highly Efficient Ferrocene‐Based Amino‐Phosphine‐Alcohol (f‐Amphol) Ligands for Iridium‐Catalyzed Asymmetric Hydrogenation of Simple Ketones
Authors: Yu Jianfei , Duan Meng , Wu Weilong , Qi Xiaotian , Xue Peng , Lan Yu , Dong Xiu‐Qin , Zhang Xumu
Published: November 2016

We have successfully developed a series of novel and modular ferrorence‐based amino‐phosphine‐alcohol (f‐Amphol) ligands, and applied them to iridium‐catalyzed asymmetric hydrogenation of various simple ketones to afford the corresponding chiral alcohols with excellent enantioselectivities and conversions (98–99.9 % ee, >99 % conversion, turnover number up to 200 000). Control experiments and density functional theory (DFT) calculations have shown that the hydroxyl group of our f‐Amphol ligands played a key role in this asymmetric hydrogenation.
Diffusionsschweißen von Metallschäumen zur Anwendung in Latentwärmespeichern für fahrzeuggerechte Thermoelektrische Generatoren
Authors: Klein Altstedde Mirko , Gietzelt Thomas , Martin Tim , Toth Volker , Jemmali Raouf
Published: November 2016

Thermoelektrische Generatoren ermöglichen die Nutzung von Abgaswärme von Verbrennungsmotoren durch direkte Wandlung in elektrische Energie. An die Langzeitbeständigkeit der verwendeten Werkstoffe und Konstruktionen werden hohe Anforderungen gestellt und das wechselnde Wärmeangebot muss über geeignete Maßnahmen vereinheitlicht werden, bpsw. durch latente Wärmespeichermaterialien. Ein System zur Aufnahme dieses Speichermaterials, für das offenporige Metallschäume unterschiedlicher Porenweite aus austenitischem Edelstahl als Stützstrukturen mittels Diffusionsschweißen mit Gehäusestrukturen gefügt wurden, wird vorgestellt.
Nutrient release characteristics and coating homogeneity of biopolymer coated urea as a function of fluidized bed process variables
Authors: Azeem Babar , KuShaari KuZilati , Man Zakaria , Trinh Thanh H.
Published: November 2016

The present study investigates the effect of fluid‐bed process parameters on the diffusion coefficient of nitrogen release and coating homogeneity of controlled‐release urea (CRU) produced in a rotary fluidized bed using polyvinyl‐alcohol‐modified starch as a coating material. An existing mathematical model was used to estimate the diffusion coefficient. The coefficient of variance of size distribution and coating mass variation are reported as a measure of coating homogeneity.

Statistical analysis suggested that the most influential process variables that govern urea release characteristics and coating homogeneity were (a) fluidizing gas temperature and (b) coating time. A moderate spray rate combined with longer coating time yielded the lowest diffusion coefficient for nutrient release. Elutriation as the result of elevated fluidizing gas temperature allowed a higher diffusion coefficient due to lower coating thickness. Burst release patterns were observed for granules with coating imperfections. The augmented temperature of fluidizing gas had a negative effect on coating mass and size distribution of CRU granules but the influence of longer coating time was positive.
Modelling of dynamic mass transfer in a vapour extraction heavy oil recovery process
Authors: Wang Qiong , Jia Xinfeng , Chen Zhangxin
Published: November 2016

Viscosity reduction through solvent dissolution into heavy oil is one of the most important recovery mechanisms of a vapour extraction (VAPEX) process. Existing analytical models can neither accurately describe the mass transfer between solvent vapour and heavy oil nor predict the solvent chamber evolution. Simulation models are confounded by numerical dispersion and have difficulty in accurately characterizing fluid properties in VAPEX. This study first develops a mass transfer model to describe a dynamic heavy oil‐solvent mixing process. This model is then incorporated into a VAPEX model to estimate solvent chamber development and an oil production rate. Diffusivity is determined through history matching theoretically calculated and experimentally measured cumulative oil production data. It is found that both constant and variable diffusivities can achieve an excellent match in cumulative oil production data. However, their respective characterization of the fluid properties in the VAPEX transition zone is very different. This study also proposes a method to convert constant diffusivity into its equivalent variable diffusivity for VAPEX by using some regressed correlations. Moreover, the back‐calculated effective diffusivity is found to be about 10–30 times of the corresponding molecular diffusivity measured in the laboratory.
Role of Sn in Ni‐Sn/CeO2 Catalysts for Ethanol Steam Reforming
Authors: Tian Hao , Li Xinyu , Chen Sai , Zeng Liang , Gong Jinlong
Published: November 2016

Reducible oxides (e.g., CeO2 and ZrO2) supported 3d transition metals (e.g., Ni, Co, Pt) exhibit remarkable catalytic activity in reactions that involve water activation, such as steam reforming and water gas shift. This paper describes the influence of Sn addition on the performance of Ni/CeO2 catalysts in ethanol steam reforming. 0.25 wt% Sn addition improved the stability of Ni/CeO2 by forming Ni‐Sn bimetallic nanoparticles with Sn enriched surfaces to suppress the carbon deposition. Ni0.25Sn/CeO2 kept over 90% ethanol conversion in a 20 h stability test at 600 °C with over 60% hydrogen selectivity under a gas hourly space velocity of 57000 mL/(g•h). However, the presence of Sn decreased the overall oxygen storage capacity and oxygen mobility of NiSn/CeO2, which hampered water activation process and coke elimination occurring at the interface between Ni and CeO2. Additionally, ethanol decomposition was also suppressed due to the coverage of Sn atoms on Ni surfaces.
Quantitative MALDI‐MS Binding Assays: An Alternative to Radiolabeling
Authors: Rossato Maxime , Miralles Guillaume , M'Kadmi Céline , Maingot Mathieu , Amblard Muriel , Mouillac Bernard , Gagne Didier , Martinez Jean , Subra Gilles , Enjalbal Christine , Cantel Sonia
Published: November 2016

Radiolabeling of ligands is still the gold standard in the study of high‐affinity receptor–ligand interactions. In an effort toward safer and simpler alternatives to the use of radioisotopes, we developed a quantitative and highly sensitive matrix‐assisted laser desorption ionization mass spectrometry (MALDI‐MS) method that relies on the use of chemically tagged ligands designed to be specifically detectable when present as traces in complex biological mixtures such as cellular lysates. This innovative technology allows easy, sensitive detection and accurate quantification of analytes at the sub‐nanomolar level. After statistical validation, we were able to perform pharmacological evaluations of G protein‐coupled receptor (V1A‐R)–ligand interactions. Both saturation and competitive binding assays were successfully processed.
Design and Synthesis of Selurampanel, a Novel Orally Active and Competitive AMPA Receptor Antagonist
Authors: Orain David , Tasdelen Engin , Haessig Samuel , Koller Manuel , Picard Anne , Dubois Celine , Lingenhoehl Kurt , Desrayaud Sandrine , Floersheim Phillip , Carcache David , Urwyler Stephan , Kallen Joerg , Mattes Henri
Published: November 2016

A series of potent quinazolinedione sulfonamide antagonists of the α‐amino‐3‐hydroxy‐5‐methyl‐4‐isoxazole‐propionic acid (AMPA) receptor were designed and synthesized. The structure–activity relationships (SAR) and in vivo activity of the series were investigated. In particular, compound 1 S (selurampanel; N‐[7‐isopropyl‐6‐(2‐methylpyrazol‐3‐yl)‐2,4‐dioxo‐1H‐quinazolin‐3‐yl]methanesulfonamide) has shown excellent oral potency against maximal electroshock seizure (MES)‐induced generalized tonic–clonic seizures in rodents as well as significant activity in patients suffering from various forms of epilepsy. The X‐ray crystal structure of selurampanel bound to the AMPA receptor hGluA was also obtained.
Assessment of Bromodomain Target Engagement by a Series of BI2536 Analogues with Miniaturized BET‐BRET
Authors: Koblan Luke W. , Buckley Dennis L. , Ott Christopher J. , Fitzgerald Mark E. , Ember Stuart W. J. , Zhu Jin‐Yi , Liu Shuai , Roberts Justin M. , Remillard David , Vittori Sarah , Zhang Wei , Schonbrunn Ernst , Bradner James E.
Published: November 2016

Evaluating the engagement of a small molecule ligand with a protein target in cells provides useful information for chemical probe optimization and pharmaceutical development. While several techniques exist that can be performed in a low‐throughput manner, systematic evaluation of large compound libraries remains a challenge. In‐cell engagement measurements are especially useful when evaluating compound classes suspected to target multiple cellular factors. In this study we used a bioluminescent resonant energy transfer assay to assess bromodomain engagement by a compound series containing bromodomain‐ and kinase‐biasing polypharmacophores based on the known dual BRD4 bromodomain/PLK1 kinase inhibitor BI2536. With this assay, we discovered several novel agents with bromodomain‐selective specificity profiles and cellular activity. Thus, this platform aids in distinguishing molecules whose cellular activity is difficult to assess due to polypharmacologic effects.
Screening for depression in cancer patients receiving radiotherapy: Feasibility and identification of effective tools in the NRG Oncology RTOG 0841 trial
Authors: Wagner Lynne I. , Pugh Stephanie L. , Small William , Kirshner Jeffrey , Sidhu Kulbir , Bury Martin J. , DeNittis Albert S. , Alpert Tracy E. , Tran Binh , Bloom Beatrice F. , Mai Julie , Yeh Alexander , Sarma Kalika , Becker Mark , James Jennifer , Bruner Deborah Watkins
Published: November 2016

BACKGROUND

Brief tools are needed to screen oncology outpatients for depressive symptoms.

METHODS

Patients starting radiotherapy for the first diagnosis of any tumor completed distress screening tools, including the 9‐item Patient Health Questionnaire (PHQ‐9), the 2‐item Patient Health Questionnaire (PHQ‐2), the National Comprehensive Cancer Network Distress Thermometer (NCCN‐DT), and the Hopkins Symptom Checklist (HSCL) (25‐item version). Patients exceeding validated cutoff scores and a systematic sample of patients whose screening was negative completed the Structured Clinical Interview for DSM‐IV (SCID) mood disorder modules via telephone.

RESULTS

Four hundred sixty‐three patients from 35 community‐based radiation oncology sites and 2 academic radiation oncology sites were recruited. Sixty‐six percent of the 455 eligible patients (n = 299) were women, and the eligible patients had breast (45%), gastrointestinal (11%), lung (10%), gynecologic (6%), or other cancers (27%). Seventy‐five (16.5%) exceeded screening cutoffs for depressive symptoms. Forty‐two of these patients completed the SCID. Another 37 patients whose screening was negative completed the SCID. Among the 79 patients completing the SCID, 8 (10.1%) met the criteria for major depression, 2 (2.5%) met the criteria for dysthymia, and 6 (7.6%) met the criteria for an adjustment disorder. The PHQ‐2 demonstrated good psychometric properties for screening for mood disorders with a cutoff score of ≥3 (receiver operating characteristic area under the curve [AUC], 0.83) and was comparable to the PHQ‐9 ( > 9; AUC = 0.85). The NCCN‐DT did not detect depression (AUC = 0.59).

CONCLUSIONS

The PHQ‐2 demonstrated good psychometric properties for screening for mood disorders, which were equivalent to the PHQ‐9 and superior to the NCCN‐DT. These findings support using the PHQ‐2 to identify patients in need of further assessment for depression, which has a low prevalence but is a clinically significant comorbidity. These findings could inform the implementation of distress screening accreditation standards. Cancer 2017;123:485–493. © 2016 American Cancer Society.
“…That which we call a rose…”: A critical analysis of rapid on‐site evaluation
Authors: Zakowski Maureen F.
Published: November 2016

Rapid on‐site evaluation (ROSE) is a term used in cytology. A PubMed search demonstrates a plethora of articles regarding ROSE, much of it outside the cytology literature and written without the input of cytologists. The purpose of this commentary is to provide an overview of the current state of the literature regarding this component of cytology practice and to introduce a few suggestions that may aid in the evaluation of the usefulness of ROSE.
Spatial distribution of synapses on tyrosine hydroxylase–expressing juxtaglomerular cells in the mouse olfactory glomerulus
Authors: Kiyokage Emi , Kobayashi Kazuto , Toida Kazunori
Published: November 2016

Olfactory sensory axons converge in specific glomeruli where they form excitatory synapses onto dendrites of mitral/tufted (M/T) and juxtaglomerular (JG) cells, including periglomerular (PG), external tufted (ET), and superficial‐short axon cells. JG cells consist of heterogeneous subpopulations with different neurochemical, physiological, and morphological properties. Among JG cells, previous electron microscopic (EM) studies have shown that the majority of synaptic inputs to tyrosine hydroxylase (TH)‐immunoreactive neurons were asymmetrical synapses from olfactory nerve (ON) terminals. However, recent physiological results revealed that 70% of dopaminergic/γ‐aminobutyric acid (GABA)ergic neurons received polysynaptic inputs via ET cells, whereas the remaining 30% received monosynaptic ON inputs. To understand the discrepancies between EM and physiological data, we used serial EM analysis combined with confocal laser scanning microscope images to examine the spatial distribution of synapses on dendrites using mice expressing enhanced green fluorescent protein under the control of the TH promoter. The majority of synaptic inputs to TH‐expressing JG cells were from ON terminals, and they preferentially targeted distal dendrites from the soma. On the other hand, the numbers of non‐ON inputs were fewer and targeted proximal dendrites. Furthermore, individual TH‐expressing JG cells formed serial synapses, such as M/T→TH→another presumed M/T or ON→TH→presumed M/T, but not reciprocal synapses. Serotonergic fibers also associated with somatic regions of TH neurons, displaying non‐ON profiles. Thus, fewer proximal non‐ON synapses provide more effective inputs than large numbers of distal ON synapses and may occur on the physiologically characterized population of dopaminergic‐GABAergic neurons (70%) that receive their most effective inputs indirectly via an ON→ET→TH circuit. J. Comp. Neurol. 525:1059–1074, 2017. © 2017 Wiley Periodicals, Inc.
Synaptic distribution of individually labeled mitral cells in the external plexiform layer of the mouse olfactory bulb
Authors: Matsuno Takeshi , Kiyokage Emi , Toida Kazunori
Published: November 2016

Mitral cells are the major projection neurons of the olfactory bulb. They receive olfactory inputs, regulate information, and project their axons to the olfactory cortex. To understand output regulation of mitral cells better, we established a method to visualize individual projection neurons and quantitatively examined their synaptic distribution. Individual mitral cells were labeled by viral injection, reconstructed three dimensionally with light microscopy, and serial sectioned for electron microscopy. Synaptic distributions were analyzed in electron microscopically reconstructed cell bodies, two regions of secondary dendrites (near the somata and ∼200 μm from the somata), and primary dendrites. The ratio of presynaptic sites (60%) and reciprocal synapses (60% presynaptic and 80% postsynaptic sites) were similar in each region. Characteristically, primary dendrite synapses were distributed mainly within the inner half of the external plexiform layer (EPL). For comparison, tufted cells were also examined, and the synaptic distribution in two secondary dendrite regions, which corresponded with mitral cells, was analyzed. The results showed that the ratio of reciprocal synapses (80% presynaptic and 90% postsynaptic sites) was greater than in mitral cells. The distribution of symmetrical synapses was also analyzed with synaptic and neuronal markers, such as parvalbumin, vesicular gamma‐aminobutyric acid transporter, and gephyrin. Parvalbumin‐expressing neurons tended to form synapses on secondary dendrites near the somata and were more uniformly distributed on primary dendrites of mitral cells. These results indicate that local mitral cell synaptic circuits are formed in accordance with their functional roles and restricted to the inner half of the EPL. J. Comp. Neurol. 525:1633–1648, 2017. © 2016 Wiley Periodicals, Inc.
Long Time Stability for Solutions of a β‐Plane Equation
Authors: Elgindi Tarek M. , Widmayer Klaus
Published: November 2016

We prove stability for arbitrarily long times of the zero solution for the so‐called β‐plane equation, which describes the motion of a two‐dimensional inviscid, ideal fluid under the influence of the Coriolis effect. The Coriolis force introduces a linear dispersive operator into the two‐dimensional incompressible Euler equations, thus making this problem amenable to an analysis from the point of view of nonlinear dispersive equations. The dispersive operator, , exhibits good decay, but has numerous unfavorable properties, chief among which are its anisotropy and its behavior at small frequencies.© 2016 Wiley Periodicals, Inc.
Secure combinatorial key predistribution scheme for sensor networks by regulating frequencies: magneto optic sensors
Authors: Sarkar Pinaki , Chowdhury Morshed Uddin , Sakurai Kouichi
Published: November 2016

Low cost, decentralized architecture and ad hoc nature are a few desirable properties of wireless sensor networks that make them well suited for gathering sensitive information in hazardous deployment grounds. Existing security protocols exploit various cryptographic tools to strengthen their security. Not many works focus on constraints faced by an adversary. One such constraint being practical difficulties to trace a particular frequency band from a large range of unknown frequencies, specially in unharmonious geographical locations. Our research capitalizes on this weakness encountered by an adversary and preassigns nodes with multiple frequency bands from a wide range of frequencies allocated to the network. Deployed nodes can discover these bands during set network setup phase by a simple trick. Nodes are to internally switch their frequency bands depending on parametric variation that are caused by an (external) impulse. Experiments conducted using magneto optic sensors confirm that any variation of their parameter affects frequencies of emergent waves. Similar behavior is expected from application specific sensors. Frequency regulation (FR) concept is applied to combinatorial key predistribution schemes (KPS) having (regular) degreer. Depending onrand each node's capability to switch internal frequencies, nodes are preallocated withnfrequency bands. This naturally partitions the (distributed) network and results in improved resilience. Combining our FR concept to a KPS where the number of shared key between a pair of nodes is at most one (γ≤ 1) may yield best case scenario of an ideally resilient key predistribution. Our analysis of systems that combines FR idea with KPS whereγ > 1 leads to an optimized key‐band distribution argument and drastic resilience improvements. Results of simulations conducted assuming real‐life scenario ascertain our analysis and establishes superior performance of our protocols as compared to prominent ones.
Synthesis of bis‐Isoxazole‐bis‐Methylene Dinitrate: A Potential Nitrate Plasticizer and Melt‐Castable Energetic Material
Authors: Wingard Leah A. , Guzmán Pablo E. , Johnson Eric C. , Sabatini Jesse J. , Drake Gregory W. , Byrd Edward F. C.
Published: November 2016

The efficient and scalable synthesis of 3,3′‐bis‐isoxazole‐5,5′‐bis‐methylene dinitrate and its energetic properties are described. The material has favorable sensitivity properties; energetic properties point toward its potential as both a melt‐castable secondary explosive and as a propellant plasticizer.
Phenylene‐Bridged Expanded Porphyrazines
Authors: Iizuka Fumiya , Kage Yuto , Kobayashi Nagao , Furuta Hiroyuki , Shimizu Soji
Published: November 2016

Novel expanded porphyrazines comprising o‐ and p‐phenylene units were synthesized from self‐condensation reactions of acyclic [2+1]‐type precursors prepared from 1,3‐diiminoisoindoline and the corresponding phenylenediamines. Möbius and Hückel topological structures of [4+2]‐type and [3+2]‐type expanded porphyrazines, respectively, were elucidated by X‐ray crystallography. Despite the Möbius and Hückel [4n]π‐electron systems, these expanded porphyrazines are virtually nonaromatic as a result of their flexible structures in solution, which may diminish intrinsic aromaticity and antiaromaticity.
Thermal induced structural properties of silver(I) sulphate (Ag2SO4)
Authors: Larsen Helge B. , Thorkildsen Gunnar , Nicholson David G. , Pattison Philip
Published: November 2016

The crystal structures of silver(I) sulphate, Ag2SO4, have been investigated as a function of temperature. A main feature is the phase transition from the low‐temperature ordered phase, F ddd, to the high‐temperature disordered phase, . In particular, the high‐temperature structure is solved from single crystal synchrotron X‐ray measurements. In this phase the title compound undergoes a colossal (anisotropic) thermal expansion of . This is presumably owing to a high anisotropic vibration state of one of the two crystallographically independent Ag‐atoms. Simultaneously occurring high ionic conductivity may be associated with silver ions moving along the ‐axis using a “paddle‐wheel” assisted percolative mechanism. Onset of metallic silver in the single crystals is documented, seemingly dependent on thermal pre‐history, mosaic structure and chemical synthesis. Possible mechanisms explaining this effect, comprising disproportionation or photo‐decomposition, are suggested.
Hydrogen‐free catalytic fractionation of woody biomass
Authors: Galkin Maxim V. , Smit Arjan T. , Subbotina Elena , Artemenko Konstantin A. , Bergquist Jonas , Huijgen Wouter J. J. , Samec Joseph S. M.
Published: November 2016

The pulping industry could become a biorefinery if the lignin and hemicellulose components of the lignocellulose are valorized. Conversion of lignin into well‐defined aromatic chemicals is still a major challenge. Lignin depolymerization reactions often occur in parallel with irreversible condensation reactions of the formed fragments. Here, we describe a strategy that markedly suppresses the undesired condensation pathways and allows to selectively transform lignin into a few aromatic compounds. Notably, applying this strategy to woody biomass at organosolv pulping conditions, the hemicellulose, cellulose, and lignin were separated and in parallel the lignin was transformed into aromatic monomers. In addition, we were able to utilize a part of the lignocellulose as an internal source of hydrogen for the reductive lignin transformations. We hope that the presented methodology will inspire researchers in the field of lignin valorization as well as pulp producers to develop more efficient biomass fractionation processes in the future.
Catalytic Conversion of Carbohydrates to Levulinate Ester over Heteropolyanion‐Based Ionic Liquids
Authors: Song Changhua , Liu Sijie , Peng Xinwen , Long Jinxing , Lou Wenyong , Li Xuehui
Published: November 2016

An efficient one‐pot approach for the production of levulinate ester from renewable carbohydrates is demonstrated over heteropolyanion‐based ionic liquid (IL‐POM) catalysts with alcohols as the promoters and solvents. The relationships between the structure, acidic strength, and solubility of the IL‐POM in methanol and the catalytic performance were studied intensively. A cellulose conversion of 100 % could be achieved with a 71.4 % yield of methyl levulinate over the catalyst [PyPS]3PW12O40 [PyPS=1‐(3‐sulfopropyl)pyridinium] at 150 °C for 5 h. This high efficiency is ascribed to the reasonably high activity of the ionic liquid (IL) catalyst and reaction coupling with rapid in situ esterification of the generated levulinic acid with the alcohol promoter, which allows the insolubility of cellulose encountered in biomass conversion to be overcome. Furthermore, the present process exhibits high feedstock adaptability for typical carbohydrates and handy catalyst recovery by a simple self‐separation procedure through temperature control.
3 D Co3(PO4)2–Reduced Graphene Oxide Flowers for Photocatalytic Water Splitting: A Type II Staggered Heterojunction System
Authors: Samal Alaka , Swain Smrutirekha , Satpati Biswarup , Das Dipti Prakasini , Mishra Barada Kanta
Published: November 2016

The design, synthesis, and photoelectrochemical characterization of Co3(PO4)2, a hydrogen evolving catalyst modified with reduced graphene oxide (RGO), is reported. The 3 D flowerlike Co3(PO4)2 heterojunction system, consisting of 3 D flowerlike Co3(PO4)2 and RGO sheets, was synthesized by a one‐pot in situ photoassisted method under visible‐light irradiation, which was achieved without the addition of surfactant or a structure‐directing reagent. For the first time, Co3(PO4)2 is demonstrated to act as a hydrogen evolving catalyst rather than being used as an oxygen evolving photoanode. In particular, 3 D flowerlike Co3(PO4)2 anchored to RGO nanosheets is shown to possess dramatically improved photocatalytic activity. This enhanced photoactivity is mainly due to the staggered type II heterojunction system, in which photoinduced electrons from 3 D flowerlike Co3(PO4)2 transfer to the RGO sheets and result in decreased charge recombination, as evidenced by photoluminescence spectroscopy. The band gap of Co3(PO4)2 was calculated to be 2.35 eV by the Kubelka–Munk method. Again, the Co3(PO4)2 semiconductor displays n‐type behavior, as observed from Mott–Schottky measurements. These RGO–Co3(PO4)2 conjugates are active in the visible range of solar light for water splitting and textile dye degradation, and can be used towards the development of greener and cheaper photocatalysts by exploiting solar light.
Electrochemical and Resonance Raman Spectroscopic Studies of Water‐Oxidizing Ruthenium Terpyridyl–Bipyridyl Complexes
Authors: Keidel Anke , López Isidoro , Staffa Jana , Kuhlmann Uwe , Bozoglian Fernando , Gimbert‐Suriñach Carolina , Benet‐Buchholz Jordi , Hildebrandt Peter , Llobet Antoni
Published: November 2016

The irreversible conversion of single‐site water‐oxidation catalysts (WOC) into more rugged catalysts structurally related to [(trpy)(5,5′‐X2‐bpy)RuIV(μ‐O)RuIV(trpy)(O)(H2O)]4+ (X=H, 1‐dn4+; X=F, 2‐dn4+; bpy=2,2′‐bipyridine; trpy=2,2′:6′,2“‐terpyridine) represents a critical issue in the development of active and durable WOCs. In this work, the electrochemical and acid–base properties of 1‐dn4+ and 2‐dn4+ were evaluated. In situ resonance Raman spectroscopy was employed to characterize the species formed upon the stoichiometric oxidation of the single‐site catalysts and demonstrated the formation of high‐oxidation‐state mononuclear Ru=O and RuO−O complexes. Under turnover conditions, the dinuclear intermediates, 1‐dn4+ and 2‐dn4+ as well as the previously proposed [RuVI(trpy)(O)2(H2O)]2+ complex (32+) are formed. Complex 32+ is a pivotal intermediate that provides access to the formation of dinuclear species. Single‐crystal X‐ray diffraction analysis of the isolated complex [RuIV(O)(trpy)(5,5′‐F2‐bpy)]2+ reveals a clear elongation of the Ru−N bond trans to the oxido ligand that documents the weakness of this bond, which promotes the release of the bpy ligand and the subsequent formation of 32+.
Foot of the Wave Analysis for Mechanistic Elucidation and Benchmarking Applications in Molecular Water Oxidation Catalysis
Authors: Matheu Roc , Neudeck Sven , Meyer Franc , Sala Xavier , Llobet Antoni
Published: November 2016

The description of the foot of the wave analysis (FOWA) applied to the electrocatalytic oxidation of water to dioxygen is reported for cases where the rate determining step is first order and second order with regard to catalyst concentration, coinciding mechanistically with the so‐called water nucleophilic attack (WNA) and the interaction of two M−O units (I2M, where M represents the metal center of the catalyst), respectively. The newly adapted equations are applied to a range of relevant molecular catalysts, both in homogeneous and heterogeneous phase, and the kinetic parameters are determined, including apparent rate constants and turnover frequencies. In this respect, the application of FOWA at different catalyst concentrations allows elucidation of the reaction mechanism that operates in each case. In addition, catalytic Tafel plots are used for assessing the performance of several molecular water oxidation catalysts (WOCs) as a function of overpotential under analogous conditions, and thus can be used for benchmarking purposes. This analysis was carried out earlier for oxide‐based WOCs; however, this is the first report using molecular WOCs.
Kinetics of Levoglucosenone Isomerization
Authors: Krishna Siddarth H. , Walker Theodore W. , Dumesic James A. , Huber George W.
Published: November 2016

We studied the acid‐catalyzed isomerization of levoglucosenone (LGO) to 5‐hydroxymethylfurfural (HMF) and developed a reaction kinetics model that describes the experimental data across a range of conditions (100–150 °C, 50–100 mm H2SO4, 50–150 mm LGO). LGO and its hydrated derivative exist in equilibrium under these reaction conditions. Thermal and catalytic degradation of HMF are the major sources of carbon loss. Within the range of conditions studied, higher temperatures and shorter reaction times favor the production of HMF. The yields of HMF and levulinic acid decrease monotonically as tetrahydrofuran is added to the aqueous solvent system, indicating that water plays a role in the LGO isomerization reaction. Initial‐rate analyses show that HMF is produced solely from LGO rather than from the hydrated derivative of LGO. The results of this study are consistent with a mechanism for LGO isomerization that proceeds through hydration of the anhydro bridge, followed by ring rearrangement analogous to the isomerization of glucose to fructose.
Impact of Oxygen Deficiency on the Electrochemical Performance of K2NiF4‐Type (La1−xSrx)2NiO4−δ Oxygen Electrodes
Authors: Kravchenko Ekaterina , Zakharchuk Kiryl , Viskup Alexander , Grins Jekabs , Svensson Gunnar , Pankov Vladimir , Yaremchenko Aleksey
Published: November 2016

Perovskite‐related (La1−xSrx)2NiO4−δ (x=0.5–0.8) phases were explored for possible use as oxygen electrodes in solid electrolyte cells with a main focus on the effect of oxygen deficiency on the electrocatalytic activity. (La1−xSrx)2NiO4−δ solid solutions were demonstrated to preserve the K2NiF4‐type tetragonal structure under oxidizing conditions. Acceptor‐type substitution by Sr is compensated by the formation of oxygen vacancies and electron holes and progressively increases high‐temperature oxygen nonstoichiometry, which reaches as high as δ=0.40 for x=0.8 at 950 °C in air. The electrical conductivity of (La1−xSrx)2NiO4−δ ceramics at 500–1000 °C and p(O2)≥10−3 atm is p‐type metallic‐like. The highest conductivity, 300 S cm−1 at 800 °C in air, is observed for x=0.6. The average thermal expansion coefficients, (14.0–15.4)×10−6 K−1 at 25–900 °C in air, are sufficiently low to ensure the thermomechanical compatibility with common solid electrolytes. The polarization resistance of porous (La1−xSrx)2NiO4−δ electrodes applied on a Ce0.9Gd0.1O2−δ solid electrolyte decreases with increasing Sr concentration in correlation with the concentration of oxygen vacancies in the nickelate lattice and the anticipated level of mixed ionic–electronic conduction. However, this is accompanied by increasing reactivity between the cell components and necessitates the microstructural optimization of the electrode materials to reduce the electrode fabrication temperature.
Selective Hydrogenolysis of Glycerol to 1,3‐Propanediol: Manipulating the Frustrated Lewis Pairs by Introducing Gold to Pt/WOx
Authors: Zhao Xiaochen , Wang Jia , Yang Man , Lei Nian , Li Lin , Hou Baolin , Miao Shu , Pan Xiaoli , Wang Aiqin , Zhang Tao
Published: November 2016

A highly dispersed Au and Pt catalyst supported on WOx was developed for high performance in the selective hydrogenolysis of glycerol to 1,3‐propanediol (1,3‐PD) under very mild reaction conditions (81.4 % glycerol conversion, 51.6 % 1,3‐PD selectivity at 413 K, 1 MPa H2). The highly dispersed Au decreased the original surface Lewis‐acid sites on Pt/WOx but greatly increased its in situ generated Brønsted‐acid sites with the assistance of H2 through the formation of frustrated Lewis pairs. These in situ formed and spatially separated pairs of H+ and H− function as the active sites in glycerol conversion to 1,3‐PD.
An 11‐μ W, 9‐bit fully differential, cyclic/algorithmic ADC in 0.13 μm CMOS
Authors: Bako Niko , Fricke Kyle , Sobot Robert , Baric Adrijan
Published: November 2016

This paper describes a fully differential, cyclic, analogue‐to‐digital converter (ADC). It utilizes a 4‐bit binary weighted capacitor array to obtain 9‐bit resolution. The ADC uses an operational amplifier to suppress supply voltage variations. The operational amplifier with the slew‐rate detection is used to increase the speed of the ADC. The ADC is fabricated in IBM 0.13 μm CMOS process and occupies 650 × 850μm2 active area. At 10 kS/s sampling rate, the ADC consumes 11 μW. In order to test immunity of the ADC on the supply voltage variations, static and dynamic performance of the ADC is measured with triangular supply voltage (VDC = 1.5 V, VAC = 200mVpp, f = 1 kHz). The measured peak of differential nonlinearity and integral nonlinearity is  + 0.26/ − 0.67 and  + 0.65/ − 0.59, respectively. At 250 Hz, effective number of bit is 8.4 bits, SFDR = 66.7 dB and SNDR = 52.6 dB. Copyright © 2016 John Wiley & Sons, Ltd.