bluuebunny/crossref_metadata_2025 huggingface dataset:
Temporal variation of frictional strength in an earthquake swarm in NE Japan caused by fluid migration
Authors: Yoshida Keisuke , Hasegawa Akira , Yoshida Takeyoshi
Published: August 2016

Temporal variations of the fault frictional strength was investigated based on the diversity of focal mechanisms in the source area of the Yamagata‐Fukushima border earthquake swarm, a significant earthquake swarm that occurred in central Tohoku, NE Japan, which started just after the 2011 M9.0 Tohoku‐Oki earthquake. The focal mechanisms of events in this swarm activity were determined using P wave polarity data as well as short‐period (1.5–2.5 Hz) waveform data from the direct P wave. The stress field in the source area of this swarm was estimated by applying stress tensor inversions to these focal mechanism data. Based on the estimated stress field, and under the assumption of uniform stress, we calculated relative frictional strengths for individual focal mechanisms. The calculated relative frictional strengths vary over a wide range, but their average value exhibits a characteristic temporal variation, which is at first small, but steadily increases with time for 100 to 150 days, and then becomes approximately constant. We confirmed this characteristic temporal variation of the average relative frictional strength by assuming the stress to be nonuniform. Similar temporal variations of the average relative frictional strength are obtained for even these cases, confirming the variation. The most likely cause for the observed temporal variation of the average relative frictional strength is the temporal variation of the pore fluid pressure in the source area of the swarm, facilitated by the Tohoku‐Oki earthquake and the subsequent fluid diffusion.
Multimodel ensemble simulations of present and future climates over West Africa: Impacts of vegetation dynamics
Authors: Erfanian Amir , Wang Guiling , Yu Miao , Anyah Richard
Published: August 2016

In this study, we take an ensemble modeling approach using the regional climate model RegCM4.3.4‐CLM‐CN‐DV (RCM) to study the impact of including vegetation dynamics on model performance in simulating present‐day climate and on future climate projections over West Africa. The ensemble consists of four global climate models (GCMs) as lateral boundary conditions for the RCM, and simulations with both static and dynamic vegetation are conducted. The results demonstrate substantial sensitivity of the simulated precipitation, evapotranspiration, and soil moisture to vegetation representation. Although including dynamic vegetation in the model eliminates potential inconsistencies between surface climate and the bioclimatic requirements of the prescribed vegetation, it enhances model biases causing climate drift. For present‐day climate, the ensemble average generally outperforms individual members due to cancelation of model biases. For future changes, although the original GCMs project contradicting future rainfall trends over West Africa, the RCMs‐produced trends are generally consistent. The multimodel ensemble projects significant decreases of rainfall over a major portion of West Africa and significant increases over eastern Sahel and East Africa. Projected future changes of evapotranspiration and soil moisture are consistent with those of precipitation, with significant decreases (increases) for western (eastern) Sahel. Accounting for vegetation‐climate interactions has localized but significant impacts on projected future changes of precipitation, with a wet signal over a belt of projected increase of woody vegetation cover; the impact on the projected future changes of evapotranspiration and soil moisture over west and central Africa is much more profound.
A new classification scheme of European cyclone tracks with relevance to precipitation
Authors: Hofstätter M. , Chimani B. , Lexer A. , Blöschl G.
Published: August 2016

This paper proposes a new classification scheme of atmospheric cyclone tracks over Europe. The cyclones are classified into nine types, based on the geographic regions, the cyclones traverse before entering central Europe. The method is applied to ERA‐40 data for 1961–2002, considering all significant cyclones above a relative vorticity threshold. About 120 and 80 cyclone tracks per year are identified at sea level pressure and 700 hPa geopotential height, respectively. About 25% are Atlantic type cyclones, 25% emerge directly over central Europe, and another 25% originate from the lee of the Alps. The other types are less frequent (Mediterranean 12%, Polar 7%, Continental 2%, and Vb 4%). The track types show distinct characteristics in terms of cyclone intensity and cyclone life stage when entering central Europe. Cyclones of type Vb are, on average, the most intense cyclones over central Europe and even more intense than Atlantic cyclones in summer, pointing to their potential for generating extreme precipitation. The identified cyclones account for 46%–76% of long‐term precipitation in a focus region in central Europe. Precipitation differs significantly between cyclones, with Atlantic and Vb cyclones producing the highest and Continental and Polar cyclones producing the lowest long‐term precipitation totals. The contributions of cyclone types to total precipitation show distinct spatial patterns within central Europe. The new cyclone type catalog will be useful for identifying the relevance of specific track types for precipitation extremes in central Europe and analyze their temporal behavior in the context of climate change.
A coupled human‐natural systems analysis of irrigated agriculture under changing climate
Authors: Giuliani M. , Li Y. , Castelletti A. , Gandolfi C.
Published: August 2016

Exponentially growing water demands and increasingly uncertain hydrologic regimes due to changes in climate and land use are challenging the sustainability of agricultural water systems. Farmers must adapt their management strategies in order to secure food production and avoid crop failures. Investigating the potential for adaptation policies in agricultural systems requires accounting for their natural and human components, along with their reciprocal interactions. Yet this feedback is generally overlooked in the water resources systems literature. In this work, we contribute a novel modeling approach to study the coevolution of irrigated agriculture under changing climate, advancing the representation of the human component within agricultural systems by using normative meta‐models to describe the behaviors of groups of farmers or institutional decisions. These behavioral models, validated against observational data, are then integrated into a coupled human‐natural system simulation model to better represent both systems and their coevolution under future changing climate conditions, assuming the adoption of different policy adaptation options, such as cultivating less water demanding crops. The application to the pilot study of the Adda River basin in northern Italy shows that the dynamic coadaptation of water supply and demand allows farmers to avoid estimated potential losses of more than 10 M€/yr under projected climate changes, while unilateral adaptation of either the water supply or the demand are both demonstrated to be less effective. Results also show that the impact of the different policy options varies as function of drought intensity, with water demand adaptation outperforming water supply adaptation when drought conditions become more severe.
A Dual‐Ion Battery Constructed with Aluminum Foil Anode and Mesocarbon Microbead Cathode via an Alloying/Intercalation Process in an Ionic Liquid Electrolyte
Authors: Zhang Fan , Ji Bifa , Tong Xuefeng , Sheng Maohua , Zhang Xiaolong , Lee Chun‐Sing , Tang Yongbing
Published: August 2016

A novel dual‐ion battery constructed with aluminum foil anode and mesocarbon microbead (MCMB) cathode based on a lithium‐salt containing ionic liquid electrolyte is prepared. The working mechanism of this Al‐MCMB dual‐ion battery is demonstrated to be intercalation/deintercalation of anions into/from the MCMB cathode and AlLi alloying/dealloying at the Al anode. Owing to the good stability of ionic liquid at high working voltage and the protection of fluoroethylene carbonate additive in the electrolyte by forming stable solid electrolyte interphase film on the Al foil, the battery presents superior cycling stability at high cut‐off voltage of 4.8 V with a reversible capacity of 98 mAh g−1 after 300 cycles at 0.5 C with negligible decay. Moreover, as the Al foil is directly utilized as both anode material and current collector, the energy density of the packaged Al‐MCMB cell can be further increased, which is estimated to be 221 W h kg−1 at the power density of 109 W kg−1 and remains 185 W h kg−1 at 1141 W kg−1, much better than most commercial lithium‐ion batteries.
Curing kinetics of bio‐based epoxy resin based on epoxidized soybean oil and green curing agent
Authors: Chen Yahua , Xi Zhenhao , Zhao Ling
Published: August 2016

New thermoset with a high bio‐based content was synthesized by curing epoxidized soybean oil (ESO) with a green curing agent maleopimaric acid catalyzed by 2‐ethly‐4‐methylimidazole. Non‐isothermal differential scanning calorimetry and a relatively new integral isoconversional method were used to analyze the curing kinetic behaviors and determine the activation energy (Ea). The two‐parameter Šesták–Berggren autocatalytic model was applied in the mathematical modeling to obtain the reaction orders and the pro‐exponential factor. For anhydride/epoxy group molar ratio equal to 0.7, Ea decreased from 82.70 to 80.17 kJ/mol when increasing the amount of catalyst from 0.5 to 1.5 phr toward ESO. The reaction orders m and n were 0.4148 and 1.109, respectively. The predicted non‐isothermal curing rates of Šesták–Berggren model matched perfectly with the experimental data. © 2016 American Institute of Chemical Engineers AIChE J, 63: 147–153, 2017
Cannibalism versus funerary defleshing and disarticulation after a period of decay: comparisons of bone modifications from four prehistoric sites
Authors: Bello Silvia M. , Wallduck Rosalind , Dimitrijević Vesna , Živaljević Ivana , Stringer Chris B.
Published: August 2016

Objectives

Humanly induced modifications on human and non‐human bones from four archaeological sites of known funerary rituals (one interpreted as cannibalism and three interpreted as funerary defleshing and disarticulation after a period of decay) were analyzed to ascertain whether macromorphological and micromorphological characteristics of cut marks can be used to distinguish cannibalistic from secondary burial practices.

Material and methods

Four collections were analyzed: the Magdalenian assemblage from Gough's Cave (UK) and the Mesolithic‐Neolithic bone samples from Lepenski Vir, Padina and Vlasac (Serbia). A total of 647 cut marks (345 on human and 302 on non‐human remains) were imaged and measured using an optical surface measurement system, the Alicona InfiniteFocus, housed at the Natural History Museum (London, UK).

Results

The frequency of cut marks at Gough's Cave exceeds 65%, while it is below 1% in the Serbian sites, and no human tooth marks and only one case of percussion damage have been observed on the three Serbian collections. The distribution of cut marks on human bones is comparable in the four assemblages. Cannibalized human remains, however, present a uniform cut mark distribution, which can be associated with disarticulation of persistent and labile articulations, and the scalping and filleting of muscles. For secondary burials where modification occurred after a period of decay, disarticulation marks are less common and the disarticulation of labile joints is rare. The micromorphometric analyses of cut marks on human and non‐human remains suggest that cut marks produced when cleaning partially decayed bodies are significantly different from cut marks produced during butchery of fresh bodies.

Conclusions

A distinction between cannibalism and secondary treatment of human bodies can be made based on frequency, distribution and micromorphometric characteristics of cut marks.
Regioselective Dichlorination of a Non‐Activated Aliphatic Carbon Atom and Phenolic Bismethylation by a Multifunctional Fungal Flavoenzyme
Authors: Chankhamjon Pranatchareeya , Tsunematsu Yuta , Ishida‐Ito Mie , Sasa Yuzuka , Meyer Florian , Boettger‐Schmidt Daniela , Urbansky Barbara , Menzel Klaus‐Dieter , Scherlach Kirstin , Watanabe Kenji , Hertweck Christian
Published: August 2016

The regioselective functionalization of non‐activated carbon atoms such as aliphatic halogenation is a major synthetic challenge. A novel multifunctional enzyme catalyzing the geminal dichlorination of a methyl group was discovered in Aspergillus oryzae (Koji mold), an important fungus that is widely used for Asian food fermentation. A biosynthetic pathway encoded on two different chromosomes yields mono‐ and dichlorinated polyketides (diaporthin derivatives), including the cytotoxic dichlorodiaporthin as the main product. Bioinformatic analyses and functional genetics revealed an unprecedented hybrid enzyme (AoiQ) with two functional domains, one for halogenation and one for O‐methylation. AoiQ was successfully reconstituted in vivo and in vitro, unequivocally showing that this FADH2‐dependent enzyme is uniquely capable of the stepwise gem‐dichlorination of a non‐activated carbon atom on a freestanding substrate. Genome mining indicated that related hybrid enzymes are encoded in cryptic gene clusters in numerous ecologically relevant fungi.
Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 to CN under Extreme Conditions
Authors: Zheng Haiyan , Li Kuo , Cody George D. , Tulk Christopher A. , Dong Xiao , Gao Guoying , Molaison Jamie J. , Liu Zhenxian , Feygenson Mikhail , Yang Wenge , Ivanov Ilia N. , Basile Leonardo , Idrobo Juan‐Carlos , Guthrie Malcolm , Mao Ho‐kwang
Published: August 2016

Acetonitrile (CH3CN) is the simplest and one of the most stable nitriles. Reactions usually occur on the C≡N triple bond, while the C−H bond is very inert and can only be activated by a very strong base or a metal catalyst. It is demonstrated that C−H bonds can be activated by the cyano group under high pressure, but at room temperature. The hydrogen atom transfers from the CH3 to CN along the CH⋅⋅⋅N hydrogen bond, which produces an amino group and initiates polymerization to form a dimer, 1D chain, and 2D nanoribbon with mixed sp2 and sp3 bonded carbon. Finally, it transforms into a graphitic polymer by eliminating ammonia. This study shows that applying pressure can induce a distinctive reaction which is guided by the structure of the molecular crystal. It highlights the fact that very inert C−H can be activated by high pressure, even at room temperature and without a catalyst.
Rapid Synthesis of Aryl Fluorides in Continuous Flow through the Balz–Schiemann Reaction
Authors: Park Nathaniel H. , Senter Timothy J. , Buchwald Stephen L.
Published: August 2016

The Balz–Schiemann reaction remains a highly utilized means for preparing aryl fluorides from anilines. However, the limitations associated with handling aryl diazonium salts often hinder both the substrate scope and scalability of this reaction. To address this, a new continuous flow protocol was developed that eliminates the need to isolate the aryl diazonium salts. The new process has enabled the fluorination of an array of aryl and heteroaryl amines.
Synthesis, characterization, corrosion inhibition of mild steel in HCl (0.5 N) solution and solid‐state electrical conductivity of new Co(II), Ni(II), Cu(II) and Zn(II) complexes
Authors: Nassar A. M. , Hassan A. M. , Elkmash A. N.
Published: August 2016

This work consists of a study of the corrosion‐inhibiting and semiconducting properties of new binuclear Co(II), Ni(II), Cu(II) and Zn(II) complexes with a Schiff base, H2L, obtained from the 2:1 M condensation of salicylaldehyde and o‐dianisidine, respectively. Elemental, spectral and thermal analyses were used to characterize these complexes. The magnetic susceptibilities of these complexes were also determined. Weight loss, potentiodynamic polarization and scanning optical microscopy were the techniques used to investigate the efficiency of these new compounds as corrosion inhibitors. The antibacterial activity of the compounds was measured against sulfate‐reducing bacteria. It was found that inhibition occurs via the chemisorption of metal complexes on the steel surface. This absorption obeys the Langmuir adsorption isotherm model.
Study of differentiated human umbilical cord–derived mesenchymal stem cells transplantation on rat model of advanced parkinsonism
Authors: Wang Zhaowei , Chen Aimin , Yan Shengjuan , Li Chengyan
Published: August 2016

The aim of this study was to explore the curative effect of differentiated human umbilical cord–derived mesenchymal stem cells (hUC‐MSCs) transplantation on rat of advanced Parkinson disease (PD) model. Human umbilical cord–derived mesenchymal stem cells were cultured and induced differentiation in vitro. The PD rats were established and allocated randomly into 2 groups: differentiated hUC‐MSCs groups and physiological saline groups (the control group). Rotation test and immunofluorescence double staining were done. The result showed that hUC‐MSCs could differentiate into mature dopamine neurons. Frequency of rotation was significantly less in differentiated hUC‐MSCs groups than in normal saline group. After we transplanted these cells into the unilateral lesioned substantia nigra induced by striatal injection of 6‐hydroxydopamine and performed in the medial forebrain bundle and ventral tegmental area, nigral tyrosine hydroxylase–positive cells were observed and survival of at least 2 months. In addition, transplantation of hUC‐MSCs could make an obviously therapeutic effect on PD rats.
The Ganglioside GM‐1 Inhibits Bupivacaine‐Induced Neurotoxicity in Mouse Neuroblastoma Neuro2a Cells
Authors: Liang Yujie , Ji Jiemei , Lin Yunan , He Yajun , Liu Jingchen
Published: August 2016

Objective

Studies indicate that bupivacaine‐induced neurotoxicity results from apoptosis. Gangliosides have been shown to promote neuronal repair and recovery of neurological function after spinal cord injury. Previously, we confirmed that in vivo administration of the ganglioside GM‐1 attenuated bupivacaine‐induced neurotoxicity in various animal models; however, the underlying mechanism remains unclear.

Methods

Cells of the neuroblastoma line N2a (Neuro2a cells) were divided into three experimental groups: control, bupivacaine‐treated, and bupivacaine‐treated with GM‐1 pretreatment. Cell viability and apoptosis were assessed through CCK‐8 assays, Hoechst staining, and flow cytometry analysis of Annexin‐V/propidium iodide double labeling. Real‐time polymerase chain reaction and western blotting assessed the expression of caspase‐3, caspase‐8, and caspase‐9.

Results

Bupivacaine‐induced apoptosis worsened with increasing dose and exposure time. Bupivacaine induced increased expression of caspase‐3 and caspase‐9, but not caspase‐8, indicating that the mitochondrial pathway but not the death receptor apoptosis pathway was activated. GM‐1 pretreatment inhibited bupivacaine‐induced apoptosis and the expression of caspase‐3 and caspase‐9 in a dose‐dependent manner.

Conclusion

Bupivacaine induced neurotoxicity by activating apoptosis via the mitochondrial pathway, and this was inhibited by GM‐1 pretreatment.
Coumarin‐Induced DNA Ligation, Rearrangement to DNA Interstrand Crosslinks, and Photorelease of Coumarin Moiety
Authors: Sun Huabing , Fan Heli , Eom Hyeyoung , Peng Xiaohua
Published: August 2016

Coumarin moieties react with thymine and cytosine in DNA by photoinduced [2+2] cycloaddition, which allows quantitative DNA interstrand crosslink (ICL) formation. Here, we report the application of coumarin analogues for DNA photoligation and the rearrangement of coumarin‐induced ligation to ICL products. Both DNA sequences and the linker units at position 4 of the coumarin moieties affected coumarin‐induced DNA photoligation. A flexible linker unit favored DNA ICL formation but led to inefficient photoligation, whereas coumarins without linker units greatly increased DNA photoligation efficiency. DNA photoligation induced by the coumarin moiety was photoswitchable. Ligation products were formed between coumarin and dT or dC upon 350 nm irradiation but reverted to the original single‐stranded oligodeoxyribonucleotides (ODNs) upon 254 nm irradiation. Rearrangement of ligated ODNs into ICL products occurred during the switchable (350 nm/254 nm) processes. Additionally, photoinduced cleavage of coumarin 3 occurred with dC‐3 cycloadducts upon 254 nm irradiation, which was confirmed by mass spectrometry analysis.
Keep your eye on…
Authors: Knopf Alison
Published: August 2016

Psychological treatments for conduct disorder problems

Adverse effects of unregulated drug kratom
Participation in sports reduces teen risk of nonmedical use of prescription opioids and heroin
Authors: Knopf Alison
Published: August 2016

Despite the increase in both prescribing of opioids to children and adolescents and the nonmedical use of prescription opioids by this age group over the past two decades, when teens are athletes they are less likely to engage in any nonprescription opioid use, including heroin, than non‐athletes, researchers have found.
NiFe Layered‐Double‐Hydroxide‐Derived NiO‐NiFe2O4/Reduced Graphene Oxide Architectures for Enhanced Electrocatalysis of Alkaline Water Splitting
Authors: Zhang Guoquan , Li Yanfang , Zhou Yufei , Yang Fenglin
Published: August 2016

Electrochemical water splitting is an environmentally friendly technology to store renewable but intermittent energy into hydrogen fuels. Nowadays, exploiting low‐costing, high‐performance, and robust catalysts for the electrochemical oxygen evolution reaction (OER) is essential to improve the overall efficiency of water splitting. Herein, the synthesis, structural characterization, and electrocatalytic OER performance of NiO‐NiFe2O4 nanoparticles anchored on reduced graphite oxide frameworks (NiO‐NiFe2O4/rGO) were investigated. Facile thermal annealing of the NiFe layered double hydroxide (NiFe‐LDH) precursor led to the formation of highly dispersible NiO‐NiFe2O4 nanoparticles (20–30 nm in size) across the rGO substrate with a NiO/NiFe2O4 molar ratio up to 4.42. In contrast to the nanostructured NiFe‐LDH/rGO catalyst, the NiO‐NiFe2O4/rGO nanohybrid exhibits a lower OER onset potential (Eonset=1.436 V vs. RHE), affords a smaller overpotential of 296 mV, and achieves a current density of 10 mA cm−2 with a Tafel slope of about 43 mV dec−1; these values are comparable to those of the benchmark IrO2 catalyst. The synergy between the abundant catalytically active sites through good dispersion of NiO‐NiFe2O4 across the rGO substrate and fluent electron transport arising from the rGO and NiFe2O4 components results in the outstanding electrocatalytic activity. The extremely high catalytic activity, facile synthesis, and low‐cost of the NiO‐NiFe2O4/rGO nanohybrid make it a very promising catalyst for the OER.
CuAAC Click Reactions in the Gas Phase: Unveiling the Reactivity of Bis‐Copper Intermediates
Authors: Iacobucci Claudio , Lebon Alexandre , De Angelis Francesco , Memboeuf Antony
Published: August 2016

Copper‐catalysed azide alkyne cycloaddition (CuAAC) has been considered a breakthrough transformation over the last 15 years. Its debated mechanism arouses continuously growing interest. By means of a mass spectrometer modified ad hoc, the entire catalytic cycle of CuAAC reaction has been investigated in the gas phase. Ion‐molecule reactions were performed inside the mass spectrometer to reproduce step‐by‐step, at a molecular level, the complete catalytic cycle of the click reaction. We successfully challenged the reactivity of elusive mono‐ and bis‐copper intermediates by ion‐molecule reactions leading to the production of mass‐characterized triazole products, paving the way for detailed energetic studies to be performed in the gas phase. The structures of the relevant species, calculated at a DFT level, helped rationalise our experimental results.
ChemInform Abstract: High‐Performance Na3V2(PO4)3/C Cathode for Sodium‐Ion Batteries Prepared by a Ball‐Milling‐Assisted Method.
Authors: Klee Rafael , Aragon Maria Jose , Alcantara Ricardo , Tirado Jose L. , Lavela Pedro
Published: August 2016

The title composite cathode material for sodium ion batteries is prepared by wet‐ball‐milling of mixtures of NH4VO3, NaH2PO4, citric acid, and EtOH for 24 h at 300 rpm in air, followed by heating at 800 °C for 8 h under Ar.
ChemInform Abstract: One Novel Near‐Infrared Ytterbium Metal—Organic Framework Based on an Unprecedented [Yb6(μ2‐OH)2 (μ3‐OH)6]10+ Cluster.
Authors: Wen Guo‐Xuan , Wang Jian‐Fang , Wu Xue‐Qian , Pan Li‐Qing , Li Dong‐Sheng
Published: August 2016

Colorless crystals of [Yb3(pyc)2.5(OH)4(bipy)] (H2pyc: pyridine‐carboxylic acid) are hydrothermally synthesized from aqueous mixtures of Yb(NO3)3, H2pyc, bipy, and NaOH (autoclave, 180 °C, 96 h, 58% yield).
ChemInform Abstract: Zirconocenes vs. Alanes: A Crucial Choice of the Allyl Source for Highly Diastereoselective Allylzincation of Nonracemic Chiral Imines.
Authors: Coffinet Michael , Jaroschik Florian , Vasse Jean‐Luc
Published: August 2016

A diastereoselective synthesis of enantioenriched homoallyl amine derivatives (III) and (V) is developed.
ChemInform Abstract: A Two‐Component Alkyne Metathesis Catalyst System with an Improved Substrate Scope and Functional Group Tolerance: Development and Applications to Natural Product Synthesis.
Authors: Schaubach Sebastian , Gebauer Konrad , Ungeheuer Felix , Hoffmeister Laura , Ilg Marina K. , Wirtz Conny , Fuerstner Alois
Published: August 2016

A catalyst formed in situ upon mixing of a trisamidomolybdenum alkylidyne complex and a trisilanol derivative is highly efficient in metathesis reactions of a series of model compounds comprising primary, secondary or phenolic ‐OH groups, as well as challenging (bis)propargylic substrates.
ChemInform Abstract: Development and Applications of Transesterification Reactions Catalyzed by N‐Heterocyclic Olefins.
Authors: Bluemel Marcus , Noy Janina‐Miriam , Enders Dieter , Stenzel Martina H. , Nguyen Thanh V.
Published: August 2016

N‐Heterocyclic olefins represent a novel class of transesterification catalysts.
ChemInform Abstract: Construction of Stereogenic α,α‐Disubstituted Cycloalkanones via 1° Amine Thiourea Dual Catalysis: Experimental Scope and Computational Analyses.
Authors: Kang Jun Yong , Johnston Ryne C. , Snyder Kevin M. , Cheong Paul Ha‐Yeon , Carter Rich G.
Published: August 2016

The reaction mechanism, including the catalysts′ features responsible for the stereoselectivity, is extensively investigated.
ChemInform Abstract: N‐Heterocyclic Carbene‐Catalyzed Convenient Benzonitrile Assembly.
Authors: Jia Qianfa , Wang Jian
Published: August 2016

An oxidative NHC‐catalyzed cyclization of ketonitriles (I) and (IV) with α,β‐unsaturated aldehydes provides a novel method for the synthesis of functionalized benzonitriles.
ChemInform Abstract: Enantio‐ and Diastereoselective Cross‐Annulation of Enal and Ketone with New Chiral Bicyclic N‐Heterocyclic Carbene Catalysts.
Authors: Hasegawa Momo , Yoshida Kazuhiro , Yanagisawa Akira
Published: August 2016

A series of 17 new chiral bicyclic imidazolium salts are tested as catalysts for the enantio‐ and diastereoselective cross‐annulation reaction of cinnamaldehyde (I) and trifluoroacetophenone (II).
ChemInform Abstract: Regioselective Synthesis of Naphtho‐Fused Heterocycles via Palladium(0)‐Catalyzed Tandem Reaction of N‐Tosylhydrazones.
Authors: Ngo Thang Ngoc , Dang Tuan Thanh , Villinger Alexander , Langer Peter
Published: August 2016

The tandem process involves the cross‐coupling reaction of N‐tosylhydrazones with the dibromide partner followed by intramolecular 5‐exo‐trig and 3‐exo‐trig cyclizations, ring opening, and β‐hydride elimination.
ChemInform Abstract: Friedel—Crafts Alkylation of Indoles with p‐Quinols: The Role of Hydrogen Bonding of Water for the Desymmetrization of the Cyclohexadienone System.
Authors: Garcia‐Garcia Carolina , Ortiz‐Rojano Laura , Alvarez Susana , Alvarez Rosana , Ribagorda Maria , Carreno M. Carmen
Published: August 2016

5‐Indolyl substituted 4‐hydroxy‐4‐methyl‐2‐cyclohexanone systems are prepared in a high π‐facial diastereoselective manner.
ChemInform Abstract: Curtius‐Like Rearrangement of an Iron—Nitrenoid Complex and Application in Biomimetic Synthesis of Bisindolylmethanes.
Authors: Li Dashan , Wu Ting , Liang Kangjiang , Xia Chengfeng
Published: August 2016

An iron(II)‐catalyzed Curtius‐like rearrangement involving the decomposition of an iron‐nitrenoid complex generated by cleavage of N—O bonds of functionalized heteroauxin hydroxamates is investigated.
ChemInform Abstract: A Mild and Efficient Approach to Enantioenriched α‐Hydroxyethyl α,β‐Unsaturated δ‐Lactams.
Authors: Han Seo‐Jung , Stoltz Brian M.
Published: August 2016

The preparation of a potentially versatile α‐substituted α,β‐unsaturated lactam is described.
ChemInform Abstract: Base‐Controlled Cu‐Catalyzed Tandem Cyclization/Alkynylation for the Synthesis of Indolizines.
Authors: Oh Kyung Hwan , Kim Seong Min , Park Sun Young , Park Jin Kyoon
Published: August 2016

The title reaction of pyridines having an alkynyl side chain proceeds via a 5‐endo‐dig aminocupration, followed by coupling of the copper intermediate with an alkynyl bromide.
ChemInform Abstract: Regioselectively Controlled Synthesis of N‐Substituted (Trifluoromethyl)pyrimidin‐2(1H)‐ones.
Authors: da Silva Andreia M. P. W. , da Silva Fabio M. , Bonacorso Helio G. , Frizzo Clarissa P. , Martins Marcos A. P. , Zanatta Nilo
Published: August 2016

Conditions for the selective and high‐yielding preparation of either 1,4‐ or 1,6‐regioisomers of the title products are elaborated starting from 4‐substituted 1,1,1‐trifluoro‐4‐methoxybut‐3‐en‐2‐ones and nonsymmetric ureas or urea sulfates, respectively.
ChemInform Abstract: Metal Free C—H Functionalization of Diazines and Related Heteroarenes with Organoboron Species and Its Application in the Synthesis of a CDK Inhibitor, Meriolin 1.
Authors: Thatikonda Thanusha , Singh Umed , Ambala Srinivas , Vishwakarma Ram A. , Singh Parvinder Pal
Published: August 2016

A broad range of hetarenes is coupled with various aryl and hetaryl boronic acids to form the products in moderate yields.
ChemInform Abstract: Regioselective 2‐Amination of Polychloropyrimidines.
Authors: Smith Sean M. , Buchwald Stephen L.
Published: August 2016

5‐Trimethylsilyl substituted di‐ and trichloropyrimidines react with aryl‐ and alkyl amines to give regioselectively 2‐aminopyrimidines.
ChemInform Abstract: Visible‐Light Photoredox Synthesis of Chiral α‐Selenoamino Acids.
Authors: Jiang Min , Yang Haijun , Fu Hua
Published: August 2016

A simple and scalable β‐carbon coupling of N‐acetoxyphthalimide derivatives of L‐aspartic as well as L‐glutamic acid with diaryl or dialkyl diselenides is described.
ChemInform Abstract: Vanadium Electrolyte Studies for the Vanadium Redox Battery — A Review
Authors: Skyllas‐Kazacos Maria , Cao Liuyue , Kazacos Michael , Kausar Nadeem , Mousa Asem
Published: August 2016

Review: 144 refs.
ChemInform Abstract: Inorganic Nanoparticles in Porous Coordination Polymers
Authors: Kim Cho Rong , Uemura Takashi , Kitagawa Susumu
Published: August 2016

Review: 74 refs.
ChemInform Abstract: Shape‐Controlled Synthesis of Au—Pd Bimetallic Nanocrystals for Catalytic Applications
Authors: Zhang Lei , Xie Zhaoxiong , Gong Jinlong
Published: August 2016

Review: 111 refs.
ChemInform Abstract: Functionalized Hexagonal Boron Nitride Nanomaterials: Emerging Properties and Applications
Authors: Weng Qunhong , Wang Xuebin , Wang Xi , Bando Yoshio , Golberg Dmitri
Published: August 2016

Review: 205 refs.
ChemInform Abstract: Perovskite Materials in Energy Storage and Conversion
Authors: Zhu Liang , Ran Ran , Tade Moses , Wang Wei , Shao Zongping
Published: August 2016

Review: 333 refs.
ChemInform Abstract: Oxidative Aminoaziridination: Past, Present, and Future
Authors: Kuznetsov Mikhail A. , Kuznetsova Liudmila M. , Pankova Alena S.
Published: August 2016

Review: [67 refs.
ChemInform Abstract: C—C Bond Forming Reactions Catalyzed by Chiral Metalloporphyrins
Authors: Rybicka‐Jasinska Katarzyna , Ciszewski Lukasz W. , Gryko Daniel T. , Gryko Dorota
Published: August 2016

Review: 74 refs.
ChemInform Abstract: Homogeneous Metal‐Based Catalysis in Supercritical Carbon Dioxide as Reaction Medium
Authors: Olmos Andrea , Asensio Gregorio , Perez Pedro J.
Published: August 2016

Review: 178 refs.
ChemInform Abstract: Engineering and Manufacturing of Pharmaceutical Co‐Crystals: A Review of Solvent‐Free Manufacturing Technologies
Authors: Ross S. A. , Lamprou D. A. , Douroumis D.
Published: August 2016

Review: 138 refs.
ChemInform Abstract: Poly(ADP‐ribose): From Chemical Synthesis to Drug Design
Authors: Drenichev Mikhail S. , Mikhailov Sergey N.
Published: August 2016

Review: 64 refs.
ChemInform Abstract: Quantum Confined Colloidal Nanorod Heterostructures for Solar‐to‐Fuel Conversion
Authors: Wu Kaifeng , Lian Tianquan
Published: August 2016

Review: 293 refs.
ChemInform Abstract: Marriage of Heavy Main Group Elements with π‐Conjugated Materials for Optoelectronic Applications
Authors: Parke Sarah M. , Boone Michael P. , Rivard Eric
Published: August 2016

Review: 179 refs.
Development of Potent and Metabolically Stable APJ Ligands with High Therapeutic Potential
Authors: Juhl Cathleen , Els‐Heindl Sylvia , Schönauer Ria , Redlich Gorden , Haaf Erik , Wunder Frank , Riedl Bernd , Burkhardt Nils , Beck‐Sickinger Annette G. , Bierer Donald
Published: August 2016

The apelin ligand receptor system is an important target to develop treatment strategies for cardiovascular diseases. Although apelin exhibits strong inotropic effects, its pharmaceutical application is limited because no agonist with suitable properties is available. On the one hand, peptide ligands are too instable, and on the other hand, small‐molecule agonists show only low potency. This study describes the development of apelin (APJ) receptor agonists with not only high activity but also metabolic stability. Several strategies including capping of termini, insertion of unnatural amino acids, cyclization, and lipidation were analyzed. Peptide activity was tested using a Ca2+‐mobilization assay and the degradation of selected analogues was analyzed in rat plasma. The best results were obtained by N‐terminal lipidation of a 13‐mer apelin derivative. This analogue displayed a half‐life of 29 h in rat plasma, compared with 0.025 h for the wild‐type peptide. Furthermore, in vivo pharmacokinetics revealed a clearance of 0.049 L h−1 kg−1 and a half‐life of 0.36 h. In summary, amino acid substitution and fatty acid modification resulted in a potent and 1000‐fold more stable peptide that exhibits high pharmaceutical potential.
Preclinical evaluation of [111In]MICA‐401, an activity‐based probe for SPECT imaging of in vivo uPA activity
Authors: Vangestel Christel , Thomae David , Van Soom Jeroen , Ides Johan , wyffels Leonie , Pauwels Patrick , Stroobants Sigrid , Van der Veken Pieter , Magdolen Viktor , Joossens Jurgen , Augustyns Koen , Staelens Steven
Published: August 2016

Urokinase‐type plasminogen activator (uPA) and its inhibitor PAI‐1 are key players in cancer invasion and metastasis. Both uPA and PAI‐1 have been described as prognostic biomarkers; however, non‐invasive methods measuring uPA activity are lacking. We developed an indium‐111 (111In)‐labelled activity‐based probe to image uPA activity in vivo by single photon emission computed tomography (SPECT). A DOTA‐conjugated uPA inhibitor was synthesized and radiolabelled with 111In ([111In]MICA‐401), together with its inactive, hydrolysed form ([111In]MICA‐402). A biodistribution study was performed in mice (healthy and tumour‐bearing), and tumour‐targeting properties were evaluated in two different cancer xenografts (MDA‐MB‐231 and HT29) with respectively high and low levels of uPA expression in vitro, with either the active or hydrolysed radiotracer. MicroSPECT was performed 95 h post injection followed by ex vivo biodistribution. Tumour uptake was correlated with human and murine uPA expression determined by ELISA and immunohistochemistry (IHC). Biodistribution data with the hydrolysed probe [111In]MICA‐402 showed almost complete clearance 95 h post injection. The ex vivo biodistribution and SPECT data with [111In]MICA‐401 demonstrated similar tumour uptakes in the two models: ex vivo 5.68 ± 1.41%ID/g versus 5.43 ± 1.29%ID/g and in vivo 4.33 ± 0.80 versus 4.86 ± 1.18 for MDA‐MB‐231 and HT‐29 respectively. Human uPA ELISA and IHC showed significantly higher uPA expression in the MDA‐MB‐231 tumours, while mouse uPA staining revealed similar staining intensities of the two tumours. Our data demonstrate non‐invasive imaging of uPA activity in vivo, although the moderate tumour uptake and hence potential clinical translation of the radiotracer warrants further investigation. Copyright © 2016 John Wiley & Sons, Ltd.
Catalytic Oxygen Evolution from Manganese Complexes with an Oxidation‐Resistant N,N,O‐Donor Ligand
Authors: Michaelos Thoe K. , Lant Hannah M. C. , Sharninghausen Liam S. , Craig Stephanie M. , Menges Fabian S. , Mercado Brandon Q. , Brudvig Gary W. , Crabtree Robert H.
Published: August 2016

There is great interest in developing Mn water‐splitting catalysts due to their low cost, abundance, and relevance to the oxygen‐evolving complex (OEC). Three ligands with highly donating pyridine alkoxide moieties, including 2‐(pyridin‐2‐yl)propan‐2‐ol (pyalkH), 2,2′‐(pyridine‐2,6‐diyl)bis(propan‐2‐ol) (py‐dialkH2), and 2‐[(2,2′‐bipyridin)‐6‐yl]propan‐2‐ol (bipy‐alkH), have been screened with Mn for oxygen‐evolution catalysis. Complexes with the ligand bipy‐alkH were shown to evolve O2 when driven by Oxone (potassium peroxymonosulfate). The catalytic mixture generated from the precursor complex [Mn(bipy‐alkH)Cl2] retained activity in unbuffered solution beyond 160 h.
Harmonizing Global Biospecimen Consent Practices to Advance Translational Research: A Call to Action
Authors: Warner AW , Moore H , Reinhard D , Ball LA , Knoppers BM
Published: August 2016

One of the many challenges of translational medicine is working with research participants to donate biospecimens through an ethical informed consent framework. The increasingly complex ethical and regulatory differences across jurisdictions translates into limitations on use and potential value of biological specimens and their associated data in clinical research. We introduce a call to action for more uniform global standards for collection of biological specimen informed consent data to enable greater advancements in medical research.
From Barley Straw to Valuable Polyols: A Sustainable Process Using Ethanol/Water Mixtures and Hydrogenolysis over Ruthenium‐Tungsten Catalyst
Authors: Fabičovicová Katarína , Lucas Martin , Claus Peter
Published: August 2016

Organosolv fractionation of barley straw followed by a hydrogenolysis reaction of the resulting organosolv pulp over a heterogeneous catalyst containing ruthenium and tungsten on activated carbon (Ru‐W/AC) is a potential pathway to produce valuable chemicals from lignocellulose‐based feedstock in a future biorefinery. Polyols, such as ethylene glycol, propylene glycol, or 1,2‐butanediol, can be obtained with a very high yield of 70 % using organosolv barley pulp pretreated in a 50:50 wt % ethanol/water solution at 200 °C and a processing time of one hour. Moreover, we investigated the influence of several pretreatment parameters (e.g., solvent/water ratio, reaction temperature, and reaction time) on the pulp composition and product distribution obtained during the hydrogenolysis reaction to reduce the production of undesired side molecules. Finally, the optimal organosolv pretreatment conditions for straw were successfully transferred to other lignocellulose‐based feedstock, namely bamboo foliage and hemp shives.
Climatic controls on the isotopic composition and availability of soil nitrogen across mountainous tropical forest
Authors: Weintraub Samantha R. , Cole Rebecca J. , Schmitt Carl G. , All John D.
Published: August 2016

While tropical forests play a critical role in global carbon (C) and nitrogen (N) cycles, how their biogeochemical dynamics will respond to changes in climate, especially warming, is uncertain. To shed light on links between climate and N cycling in tropical forests, we measured bulk surface soil C and N concentrations and isotopic content at 40 forested sites spanning an 1800 m elevation transect in Central America, possessing wide variation in mean annual temperature (MAT; range = 10°C) and precipitation (MAP; range = 1.2 m). Climate and terrain attributes were extracted from gridded data sets and regressed against soil variables, and then, empirical relationships were combined with a mass balance model to scale up to the larger landscape. Across the remote study region, elevation and soil δ15N values displayed a strong negative relationship, while elevation was positively related to percent of soil C, N, and C:N ratios. As elevation was tightly correlated with MAT and MAP, soil chemical and isotopic content varied strongly with climate. For example, for every degree increase in MAT, soil δ15N values—an indicator of relative gaseous N losses—increased by a factor of 0.4, and soil C:N ratios, which affect net N mineralization and N availability, declined by a factor of 1.1. With the 40 sites binned into bioclimatic life zones, montane, premontane, and wet‐premontane transition forests showed distinct clustering of soil chemical and isotopic properties, yet forest type alone explained less variation compared to continuous elevation–climate parameters. Results of the spatially applied 15N mass balance model implied shifts in the contribution of gaseous‐to‐total N loss, from 10% or less in cool, wet high‐elevation forests to upwards of 60% at warmer, drier, low‐elevation sites. Climate variation was thus associated with significant shifts in N dynamics across this montane tropical region, yet more work is needed to decouple direct vs. indirect climatic controls. While the mechanisms deserve further study, observed shifts in indicators of N availability and gaseous loss may be useful in managing and modeling tropical forests under climate change.
New Contact Probe and Method to Measure Electrical Resistances in Battery Electrodes
Authors: Mainusch Nils , Christ Torge , Siedenburg Thammo , O'Donnell Tom , Lutansieto Meylia , Brand Peter‐Jochen , Papenburg Gerhard , Harms Nina , Temel Bilal , Garnweitner Georg , Viöl Wolfgang
Published: August 2016

Electrical resistivity is an important measure to qualify electrodes for lithium‐ion batteries. A reliable determination of conductivity is of high practical importance with regard to, for example, electrode production improvements and quality control. To complement state‐of‐the‐art measuring techniques, a new method has been developed based on a new “micron‐powder probe”. Following a simple measuring procedure, the system allows nondestructive, highly reproducible, and rapid data acquisition. In this paper, we describe the new concept thoroughly and present experimental results. These results demonstrate that an initial determination of resistance values in battery electrodes is beneficial especially if it is combined with an electrical postmortem analysis of cycled cathode disks. The outcome of our investigation is validated with regard to the electrochemical performance of cathodes in half‐cells.
Development, Status, and Prospects of Coal Tar Hydrogenation Technology
Authors: Yuan Yang , Li Dong , Zhang Linna , Zhu Yonghong , Wang Lei , Li Wenhong
Published: August 2016

China is rich in coal resources, and the production of mid‐to‐low‐temperature coal tar is increasing gradually. Due to containing more aliphatic hydrocarbons and less aromatic hydrocarbons, mid‐to‐low‐temperature coal tar is suitable for hydrogenation to produce fuel oil. Domestic mid‐to‐low‐temperature coal tar hydrogenation technologies are investigated here. All the technologies are divided into 6 steps, that is, coal tar hydrogenation technology of the light fraction, the delayed coking tar, the suspending‐bed reactor, the full‐range, the extractive wide distillate, and the boiling‐bed reactor. Focused on the technical features with a detailed analysis and comparison of different hydrogenation technologies, the main problems in the development of coal tar hydrogenation are described. The developments in process technology, coal tar refinement, and deep processing products will heavily influece the direction of coal tar hydrogenation in the future.
A Crystalline/Amorphous Cobalt(II,III) Oxide Hybrid Electrocatalyst for Lithium–Air Batteries
Authors: Khajehbashi S. Mohammad B. , Li Jiantao , Wang Manman , Xu Lin , Zhao Kangning , Wei Qiulong , Shi Changwei , Tang Chunjuan , Huang Lei , Wang Zhaoyang , Mai Liqiang
Published: August 2016

Weakening of the oxygen bond is the main intention in the design and synthesis of catalysts for the oxygen reduction reaction (ORR). Hybrid‐structured electrocatalysts are promising candidates for this purpose; however, the use of noble metals and the combination of different materials, such as graphene and metal oxides, usually limits their synthesis on the laboratory scale. Herein, we introduce an oxidation and rapid‐cooling process as a novel and facile way to synthesize a bare Co3O4 hybrid crystalline/amorphous catalyst. Characterization of this material shows that the facile synthesis process is effective in forming an amorphous layer on the crystal structure of Co3O4. The cyclic voltammetry and rotating disc electrode results in aqueous solution prove the good performance of the catalyst. A Li–air battery with this catalyst successfully sustains about 2500 h of continuous cycling (120 cycles) with an average discharge voltage of 2.80 V and a limited specific capacity of 1000 mAh g−1, which proves the high performance of this catalyst in non‐aqueous electrolyte. We show that the origin of the high catalytic performance in this hybrid structure derives from the synergistic behavior of two different active sites, and this concept facilitates the design and synthesis of electrocatalysts by rapid‐cooling synthesis for the industrial scale.
Unusual Course of Lafora Disease
Authors: Zutt Rodi , Drost Gea , Vos Yvonne J. , Elting Jan Willem , Miedema Irene , Tijssen Marina A. J. , Brouwer Oebele F. , de Jong Bauke M.
Published: August 2016

A 42‐year‐old male was admitted for refractory status epilepticus. At the age of 25, he had been diagnosed with juvenile myoclonic epilepsy. He had a stable clinical course for over a decade until a recent deterioration of behavior and epilepsy. After exclusion of acquired disorders, diagnostic work‐up included application of next‐generation sequencing (NGS), with a gene panel targeting progressive myoclonic epilepsies. This resulted in the diagnosis Lafora disease resulting from compound heterozygous NHLRC1 pathogenic variants. Although these pathogenic variants may be associated with a variable phenotype, including both severe and mild clinical course, the clinical presentation of our patient at this age is very unusual for Lafora disease. Our case expands the phenotype spectrum of Lafora disease resulting from pathogenic NHLRC1 variants and illustrates the value of using NGS in clinical practice to lead to a rapid diagnosis and guide therapeutic options.