bluuebunny/crossref_metadata_2025 huggingface dataset:
A Free‐Blockage Controlled Release System Based on the Hydrophobic/Hydrophilic Conversion of Mesoporous Silica Nanopores
Authors: Wang Wenqian , Chen Linfeng , Xu Li‐ping , Du Hongwu , Wen Yongqiang , Song Yanlin , Zhang Xueji
Published: December 2014

A pH‐responsive free‐blockage release system was achieved through controlling the hydrophobic/hydrophilic conversion of mesoporous silica nanopores. This system further presented pulsatile release with changing pH values between 4.0 and 7.0 for several cycles. This free‐blockage release system could also release antitumor agents to induce cell death after infecting tumor cells and could have the ability of continuous infection to tumor cells with high drug‐delivery efficiency and few side effects.
Impact of the Oxygen Defects and the Hydrogen Concentration on the Surface of Tetragonal and Monoclinic ZrO2 on the Reduction Rates of Stearic Acid on Ni/ZrO2
Authors: Foraita Sebastian , Fulton John L. , Chase Zizwe A. , Vjunov Aleksei , Xu Pinghong , Baráth Eszter , Camaioni Donald M. , Zhao Chen , Lercher Johannes A.
Published: December 2014

The role of the specific physicochemical properties of ZrO2 phases on Ni/ZrO2 has been explored with respect to the reduction of stearic acid. Conversion on pure m‐ZrO2 is 1.3 times more active than on t‐ZrO2, whereas Ni/m‐ZrO2 is three times more active than Ni/t‐ZrO2. Although the hydrodeoxygenation of stearic acid can be catalyzed solely by Ni, the synergistic interaction between Ni and the ZrO2 support causes the variations in the reaction rates. Adsorption of the carboxylic acid group on an oxygen vacancy of ZrO2 and the abstraction of the α‐hydrogen atom with the elimination of the oxygen atom to produce a ketene is the key to enhance the overall rate. The hydrogenated intermediate 1‐octadecanol is in turn decarbonylated to heptadecane with identical rates on all catalysts. Decarbonylation of 1‐octadecanol is concluded to be limited by the competitive adsorption of reactants and intermediate. The substantially higher adsorption of propionic acid demonstrated by IR spectroscopy and the higher reactivity to O2 exchange reactions with the more active catalyst indicate that the higher concentration of active oxygen defects on m‐ZrO2 compared to t‐ZrO2 causes the higher activity of Ni/m‐ZrO2.
Dihydrogen Catalysis of the Reversible Formation and Cleavage of CH and NH Bonds of Aminopyridinate Ligands Bound to (η5‐C5Me5)IrIII
Authors: Zamorano Ana , Rendón Nuria , López‐Serrano Joaquín , Valpuesta José E. V. , Álvarez Eleuterio , Carmona Ernesto
Published: December 2014

This study focuses on a series of cationic complexes of iridium that contain aminopyridinate (Ap) ligands bound to an (η5‐C5Me5)IrIII fragment. The new complexes have the chemical composition [Ir(Ap)(η5‐C5Me5)]+, exist in the form of two isomers (1+ and 2+) and were isolated as salts of the BArF− anion (BArF=B[3,5‐(CF3)2C6H3]4). Four Ap ligands that differ in the nature of their bulky aryl substituents at the amido nitrogen atom and pyridinic ring were employed. In the presence of H2, the electrophilicity of the IrIII centre of these complexes allows for a reversible prototropic rearrangement that changes the nature and coordination mode of the aminopyridinate ligand between the well‐known κ2‐N,N′‐bidentate binding in 1+ and the unprecedented κ‐N,η3‐pseudo‐allyl‐coordination mode in isomers 2+ through activation of a benzylic CH bond and formal proton transfer to the amido nitrogen atom. Experimental and computational studies evidence that the overall rearrangement, which entails reversible formation and cleavage of HH, CH and NH bonds, is catalysed by dihydrogen under homogeneous conditions.
Highly Enantioselective [3+2] Cycloaddition of Vinylcyclopropane with Nitroalkenes Catalyzed by Palladium(0) with a Chiral Bis(tert‐amine) Ligand
Authors: Wei Feng , Ren Chuan‐Li , Wang Dong , Liu Li
Published: December 2014

An enantioselective [3+2] cycloaddition of vinyl cyclopropane derived from 1,3‐indanedione with nitroalkenes catalyzed by palladium(0) with a chiral bis(tert‐amine) ligand was developed in high yields with good diastereoselectivities and excellent enantioselectivities. The resulting bis(tert‐amine)–palladium complex proved to be a highly efficient catalyst for this cycloaddition.
On the Reactivity of Tetrakis(trifluoromethyl)cyclopentadienone towards Carbon‐Based Lewis Bases
Authors: Holle Sigrid , Escudero Daniel , Inés Blanca , Rust Jörg , Thiel Walter , Alcarazo Manuel
Published: December 2014

The reactivitiy of tetrakis(trifluoromethyl)cyclopentadienone towards different C‐based Lewis bases, such as N‐heterocyclic carbenes (NHC), ylides and isonitriles, are reported. While sterically not hindered carbenes were found to yield kinetic adducts by regiospecific nucleophilic attack at the position adjacent to the carbonyl group of the ketone, bulkier nucleophiles afforded the thermodynamically more stable O‐bridged zwitterions. Interestingly, isonitriles were found to dimerize and trimerize under the same reaction conditions, forming bicyclic products that evolve differently depending on the nature of the substituents.
Regenerable Antioxidants—Introduction of Chalcogen Substituents into Tocopherols
Authors: Poon Jia‐fei , Singh Vijay P. , Yan Jiajie , Engman Lars
Published: December 2014

To improve the radical‐trapping capacity of the natural antioxidants, alkylthio‐, alkylseleno‐, and alkyltelluro groups were introduced into all vacant aromatic positions in β‐, γ‐ and δ‐tocopherol. Reaction of the tocopherols with electrophilic chalcogen reagents generated by persulfate oxidation of dialkyl dichalcogenides provided convenient but low‐yielding access to many sulfur and selenium derivatives, but failed in the case of tellurium. An approach based on lithiation of the appropriate bromo‐tocopherol, insertion of chalcogen into the carbon‐lithium bond, air‐oxidation to a dichalcogenide, and final borohydride reduction/alkylation turned out to be generally applicable to the synthesis of all chalcogen derivatives. Whereas alkylthio‐ and alkylseleno analogues were generally poorer quenchers of lipid peroxyl radicals than the corresponding parents, all tellurium compounds showed a substantially improved radical‐trapping activity. Introduction of alkyltelluro groups into the tocopherol scaffold also caused a dramatic increase in the regenerability of the antioxidant. In a two‐phase lipid peroxidation system containing N‐acetylcysteine as a water‐soluble co‐antioxidant the inhibition time was up to six‐fold higher than that recorded for the natural antioxidants.
ChemInform Abstract: Morphotropy and Temperature‐Driven Polymorphism in A2Th(AsO4)2 (A: Li, Na, K, Rb, Cs) Series.
Authors: Yu Na , Klepov Vladislav V. , Modolo Giuseppe , Bosbach Dirk , Suleimanov Evgeny V. , Gesing Thorsten M. , Robben Lars , Alekseev Evgeny V.
Published: December 2014

M2Th(AsO4)2 (M: Li, Na, K, Rb, Cs) single crystals are prepared by solid state reaction of Th(NO3)4, NH4H2AsO4, and MNO3 (Pt crucible, 1123—1273 K, controlled cooling).
ChemInform Abstract: Structure and Vibrational Analyses of LiP15.
Authors: Eckstein Nadine , Jantke Laura‐Alice , Faessler Thomas F. , Mink Janos , Drees Markus , Nilges Tom
Published: December 2014

The title compound is synthesized from a stoichiometric mixture of the elements in the presence of CuCl2 as a mineralizer (silica ampule, 823 K, 7 d).
ChemInform Abstract: Thermal Stability and Structures of Gaseous GeB2O4 and GeMo2O7.
Authors: Lopatin Sergey I. , Panin Andrej I. , Shugurov Sergey M. , Emelyanova Ksenia A.
Published: December 2014

Gaseous GeB2O4 (I) and GeMo2O7 (II) are generated in the vapor phase by electron impact heating of a 1:1 molar mixture of GeO2 and B2O3 or MoO3 and detected by Knudsen effusion mass spectrometry.
ChemInform Abstract: Garratt—Braverman Cyclization on Basic Alumina: A Green Protocol with Improved Selectivity.
Authors: Ghosh Debaki , Biswas Subhanip , Ghosh Koena , Basak Amit
Published: December 2014

Aryl‐ and hetaryl‐substituted bispropargyl substrates pre‐absorbed on basic alumina undergo Garratt—Braverman cyclization to afford aryl naphthalene derivatives and related compounds.
ChemInform Abstract: 2,6‐Bis(diphenylphosphino)pyridine: A Simple Ligand Showing High Performance in Palladium‐Catalyzed C—N Coupling Reactions.
Authors: Nadri Shirin , Rafiee Ezzat , Jamali Sirous , Joshaghani Mohammad
Published: December 2014

An effective method for the C—N coupling of a variety of aryl halides with anilines, N—heterocyclic aromatic amines, and a cyclic secondary amine is presented using a commercially available ligand and low catalyst loading.
ChemInform Abstract: Palladium‐Catalyzed Insertion of an Allene into an Aminal: Aminomethylamination of Allenes by C—N Bond Activation.
Authors: Hu Jianhua , Xie Yinjun , Huang Hanmin
Published: December 2014

A fundamentally novel approach for the synthesis of 1,3‐diamines by aminomethylamination of aromatic allenes with aminals is described.
ChemInform Abstract: Copper‐Catalyzed Regio‐ and Stereoselective O‐Arylation of Enolates.
Authors: Xu Ze‐Feng , Cai Chen‐Xin , Jiang Min , Liu Jin‐Tao
Published: December 2014

The reaction is very efficient with up to 98% yield, the regio‐ and stereoselectivity are excellent, and only O‐arylation product with Z‐configuration is obtained.
ChemInform Abstract: Organocatalytic Enantio‐ and Diastereoselective Conjugate Addition to Nitroolefins: When β‐Ketoamides Surpass β‐Ketoesters.
Authors: Du Haiying , Rodriguez Jean , Bugaut Xavier , Constantieux Thierry
Published: December 2014

Optimized conditions including a chiral squaramide catalyst render possible the conjugate addition of β‐ketoamides to nitroolefins to give the corresponding products with high diastereoselectivities and excellent enantioselectivities.
ChemInform Abstract: Aerobic Copper‐Catalyzed Oxidative [6C + 1C] Annulation: An Efficient Route to Seven‐Membered Carbocycles.
Authors: Liu Xiao , Zhang Lingjuan , Xu Xianxiu , Wang Shan , Pan Ling , Zhang Qian , Liu Qun
Published: December 2014

An efficient, excellent diastereoselective and mild method for the construction of seven‐membered carbocycles using readily available starting materials is developed.
ChemInform Abstract: The Direct Synthesis of N‐Alkylated Amides via a Tandem Hydration/N‐Alkylation Reaction from Nitriles, Aldoximes and Alcohols.
Authors: Wang Nana , Zou Xiaoyuan , Ma Juan , Li Feng
Published: December 2014

The iridium‐catalyzed reaction of benzonitrile (I) with n‐butylaldoxime followed by an addition of alcohol (III) and a base to the crude reaction mixture affords benzamides (IV) in high yields.
ChemInform Abstract: Methionine and Buthionine Sulfoximines: Syntheses under Mild and Safe Imidation/Oxidation Conditions.
Authors: Buglioni Laura , Bizet Vincent , Bolm Carsten
Published: December 2014

Three improved different routes for the synthesis of the title sulfoximes are presented including single‐step deprotections of three different functionalities.
ChemInform Abstract: Bismuth(III) Triflate‐Catalyzed Synthesis of Substituted 2‐Alkenylfurans.
Authors: Nitsch Dominik , Bach Thorsten
Published: December 2014

Silyl enol ethers (III) and (X) are used as an 4:1 mixture of Z‐ and E‐isomers.
ChemInform Abstract: One‐Pot Asymmetric Synthesis of Substituted Tetrahydrofurans via a Multicatalytic Benzoin/Michael/Acetalization Cascade.
Authors: He Gu , Wu Fengbo , Huang Wei , Zhou Rui , Ouyang Liang , Han Bo
Published: December 2014

The reaction fails with α‐substituted or γ‐branched enals.
ChemInform Abstract: Silica‐Supported Ceric Ammonium Nitrate Catalyzed Chemoselective Formylation of Indoles.
Authors: Tongkhan Sukanya , Radchatawedchakoon Widchaya , Kruanetr Senee , Sakee Uthai
Published: December 2014

A highly reactive formylating species generated from hexamethylenetetramine and CAN on SiO2 allows the conversion of indoles into 3‐formylindoles under mild conditions.
ChemInform Abstract: ZrCl4‐Promoted Facile Synthesis of Indole Derivatives.
Authors: Tummatorn J. , Gleeson M. P. , Krajangsri S. , Thongsornkleeb C. , Ruchirawat S.
Published: December 2014

Zirconium(IV) chloride effectively activates nitrogen extrusion from aryl azidoacrylates followed by annulation to provide indoles at low temperature and in short reaction times.
ChemInform Abstract: Rh(III)‐Catalyzed Selective Coupling of N‐Methoxy‐1H‐indole‐1‐carboxamides and Aryl Boronic Acids.
Authors: Zheng Jing , Zhang Yan , Cui Sunliang
Published: December 2014

Rh(III)‐catalyzed coupling of indole carboxamides with various arylboronic acids give either 2‐arylated products (III) and (VII), or [4 + 2]‐cyclized products (IV) and (VIII) depending on the different conditions used.
ChemInform Abstract: Intramolecular Larock Indole Synthesis for the Preparation of Tricyclic Indoles and Its Application in the Synthesis of Tetrahydropyrroloquinoline and Fargesine.
Authors: Gao Yan , Shan Dong , Jia Yanxing
Published: December 2014

This method is applicable for a broad variety of ring sizes including large rings, e.
ChemInform Abstract: Molecular Iodine Mediated Regioselective Synthesis of Pyranocoumarins and Bis‐Fused Benzo‐2H‐pyran Derivatives.
Authors: Majumdar K. C. , Sinha Biswajit , Ansary Inul , Ganai Sintu , Ghosh Debankan , Roy B. , Sridhar B.
Published: December 2014

The synthesis of the starting materials via Sonogashira‐coupling is described.
ChemInform Abstract: Copper‐Catalyzed Enantioselective Hetero‐Diels—Alder Reaction of Danishefsky′s Diene with β,γ‐Unsaturated α‐Ketoesters.
Authors: Hu Yanbin , Xu Kun , Zhang Sheng , Guo Fengfeng , Zha Zhenggen , Wang Zhiyong
Published: December 2014

The first Cu‐catalyzed asymmetric Hetero‐Diels—Alder reaction of β,γ‐unsaturated α‐ketoesters with Danishefsky′s diene under mild reaction conditions is described.
ChemInform Abstract: Laccase/2,2,6,6‐Tetramethylpiperidinoxyl Radical (TEMPO): An Efficient Catalytic System for Selective Oxidations of Primary Hydroxy and Amino Groups in Aqueous and Biphasic Media.
Authors: Diaz‐Rodriguez Alba , Martinez‐Montero Lia , Lavandera Ivan , Gotor Vicente , Gotor‐Fernandez Vicente
Published: December 2014

The reaction can be scaled up.
ChemInform Abstract: Nucleophilic Addition of Lewis Acid Complexed α‐Amino Carbanions to Arynes: Synthesis of 1‐Aryl‐N‐methyl‐1,2,3,4‐tetrahydroisoquinolines.
Authors: Singh Kamal Nain , Singh Paramjit , Sharma Esha , Deol Yadwinder Singh
Published: December 2014

The method is applied to the synthesis of all three alkaloids of Cryptostylis fulva, namely cryptosyline I (IXc), II (IXa) and III (IXb).
ChemInform Abstract: Reaction of N‐Propargylic β‐Enaminones with Acetylene Dicarboxylates: Catalyst‐Free Synthesis of 3‐Azabicyclo[4.1.0]hepta‐2,4‐dienes.
Authors: Goutham Kommuru , Nagaraju Vemu , Suresh Surisetti , Raghavaiah Pallepogu , Karunakar Galla V.
Published: December 2014

The title reaction proceeds under novel and exceptional base‐ and catalyst‐free conditions in a single step.
ChemInform Abstract: Substituted Benzoquinazolinones. Part 1. Synthesis of 6‐Aminobenzo[h]quinazolinones via Buchwald—Hartwig Amination from 6‐Bromobenzo[h]quinazolinones.
Authors: Nowak Monika , Malinowski Zbigniew , Jozwiak Andrzej , Fornal Emilia , Blaszczyk Alina , Kontek Renata
Published: December 2014

Compound (IIIb) is highly cytotoxic to HT29 cancer cells and only weakly toxic to normal lymphocytes.
ChemInform Abstract: CuO Nanoparticles Catalyzed Simple and Efficient Synthesis of 2,3‐Dihydroquinazolin‐4(1H)‐ones and Quinazolin‐4(3H)‐ones under Ultrasound Irradiation in Aqueous Ethanol under Ultrasound Irradiation in Aqueous Ethanol.
Authors: Zhang Jin , Ren Decheng , Ma Yangmin , Wang Weitao , Wu Hao
Published: December 2014

The catalyst can be recycled and reused at least 4 times without a significant loss in activity.
ChemInform Abstract: Asymmetric Synthesis of Stable α‐Aminoboronic Esters Catalyzed by N‐Heterocyclic Carbene and Copper(I) Chloride.
Authors: Chen Jinbo , Chen Ling‐yan , Zheng Yue , Sun Zhihua
Published: December 2014

The title synthesis produces a large scope of aliphatic and aromatic substituted α‐aminoboronic esters with a high degree of diastereoselectivity and good to excellent yields.
ChemInform Abstract: Targeted Synthesis of 2,3‐Disubstituted 2‐Phospholenes Using Catalytic Cycloalumination of Acetylenes.
Authors: D'yakonov Vladimir A. , Makhamatkhanova Alevtina L. , Agliullina Rina A. , Tyumkina Tat'yana V. , Dzhemilev Usein M.
Published: December 2014

Aluminacyclopentenes generated in situ from acetylenes and triethylaluminium react with phosphorous dihalides to give phospholenes (IV), which can be easily converted into the corresponding oxides and sulfides upon treatment with H2O2 or elemental sulfur.
ChemInform Abstract: A New Dihydrooxazole Antibiotic from the Fermentation Broth of Streptomyces djakartensis.
Authors: Wu Wen‐Jun , Zhang Ji‐Wen , Zhang Wen‐Juan , Wei Shao‐Peng
Published: December 2014

The new antibiotic (I) is isolated from the fermentation broth of Streptomyces djakartensis by bioassay‐guided fractionation.
ChemInform Abstract: Morphology‐Dependent Surface Chemistry and Catalysis of CeO2 Nanocrystals
Authors: Huang Weixin , Gao Yuxian
Published: December 2014

Review: 123 refs.
ChemInform Abstract: Topochemical Modifications of Mixed Metal Oxide Compounds by Low‐Temperature Fluorination Routes
Authors: Clemens Oliver , Slater Peter R.
Published: December 2014

Review: 89 refs.
ChemInform Abstract: Garnet: a Key Phase in Nature, the Laboratory, and Technology
Authors: Geiger Charles A.
Published: December 2014

Review: 32 refs.
ChemInform Abstract: Discrete Molecular Catalysts for Methane Functionalization
Authors: Gunsalus Niles J. , Konnick Michael M. , Hashiguchi Brian G. , Periana Roy A.
Published: December 2014

Review: 127 refs.
ChemInform Abstract: Tailor‐Made Rylene Arrays for High Performance N‐Channel Semiconductors
Authors: Jiang Wei , Li Yan , Wang Zhaohui
Published: December 2014

Review: 50 refs.
ChemInform Abstract: The Meeting of Two Disciplines: Organophosphorus and Green Chemistry
Authors: Keglevich Gyorgy , Greiner Istvan
Published: December 2014

Review: 95 refs.
ChemInform Abstract: Reactions of 1,2‐ & 1,4‐Dihydropyridines
Authors: Singh Sunil K. , Sharma Vivek K.
Published: December 2014

Review: 171 refs.
ChemInform Abstract: Self‐Assembly and Applications of Poly(glycidyl methacrylates) and Their Derivatives
Authors: Li Qing‐Lan , Gu Wen‐Xing , Gao Hui , Yang Ying‐Wei
Published: December 2014

Review: 166 refs.
Direct Arylation of Substituted Pyridines with Arylboronic Acids Catalyzed by Iron(II) Oxalate
Authors: Huang Yibo , Guan Dan , Wang Liang
Published: December 2014

The direct arylation of substituted pyridines with several arylboronic acids has been developed. This transformation could proceed readily at ambient temperature using inexpensive reagents: iron(II) oxalate as a catalyst, potassium persulfate as a co‐oxidant, which can afford the arylated products in mild to good yields. The mechanism is presumed to proceed through a nucleophilic radical addition to the pyridines with in situ reoxidation.
Design, Synthesis and Characterization of Coordination Polymer from [Cu(DMF)4(SCN)2] as a Precursor
Authors: Liu Xiaotong , Zhou Feng , Zhou Qiuxuan , Wang Lihua , Zhang Yong , Xu Qingfeng , Lu Jianmei
Published: December 2014

This paper is focused on investigation of coordination polymers constructed by Cu(II) and rigid pyridyl ligands, such as 4,4′‐bipyridyl‐1,2,4‐triazole (Hpytz) and 1,10‐phenanthroline (phen) from a mononuclear precursor [Cu(DMF)4(NCS)2] (1). As expected, the complex was self‐assembled with phen to form a 1D double‐stranded chain of [Cu(phen)(µ‐SCN)2]∞ (2), with Hpytz to form 1D zigzag chain of [Cu2(µ‐Hpytz)2(NCS)2(DMF)2(µ‐SCN)2]∞ (3) in which thiocyanate anion linked the Cu‐µ‐Hpytz‐Cu chain into an infinite 2D network via weak Cu···S interaction. To treat 3 with the bridged anion dca, a novel 3D framework [Cu(µ‐Hpytz)(µ‐dca)(µ‐SCN)] ∞ (4) was obtained in which Cu‐µ‐Hpytz‐Cu chain is preserved and both thiocyanate anion and dicyanamide (dca) act as bridging ligands. In addition, complex 3 was applied as a metal catalyst in polymerization of MMA in aqueous solution at room temperature.
Preparation of Thermosensitive Hollow Imprinted Microspheres via Combining Distillation Precipitation Polymerization and Thiol‐ene Click Chemistry
Authors: Guo Cong , Wang Bing , Shan Juanjuan
Published: December 2014

Hollow molecular imprinted polymer microspheres were prepared by distillation precipitation polymerization with (S)‐(+)‐ibuprofen (S‐IBF) as template molecule and acrylamide (AM) as functional monomer. Using the silicon dioxide (SiO2, 180 nm) modified by 3‐(trimethoxysilyl)propyl methacrylate (MPS) as the template microspheres, the molecular imprinted shells were coated on successfully (SiO2@MIPs). The thermosensitive SiO2@MIPs‐PNIPAM core‐shell microspheres were subsequently prepared by grafting the PNIPAM chains (Mn=1.21×104 g/mol, polydispersity index=1.30), which were prepared by reversible addition‐fragmentation chain transfer (RAFT) polymerization, on the surface of SiO2@MIPs microspheres via the thiol‐ene click chemistry. The grafting density of PNIPAM brushes on the SiO2@MIPs microspheres was about 0.18 chains/nm2. After HF etching, the hollow imprinted microspheres were finally obtained. For thermosensitivity analysis, the phase transition temperatures of multifunctional nanoparticles were measured by DSL at 25°C and 45°C respectively, and the sizes of the microspheres changed by about 35 nm. The modified microspheres presented excellent controlled release property to S‐IBF, moreover about half amount of the adsorptions passed into acetonitrile‐water solution through the specific holes of imprinted shell at 25°C under vibration.
Electrochemical Degradation of Triketone Herbicides and Identification of Their Main Degradation Products
Authors: Jović Milica , Manojlović Dragan , Stanković Dalibor , Gašić Uroš , Jeremić Dejan , Brčeski Ilija , Roglić Goran
Published: December 2014

The aim of this paper was the development and optimization of an electrochemical method for the degradation of two triketone herbicides, mesotrione, and sulcotrione, in a two‐electrode undivided electrochemical cell equipped with commercially available, non‐modified, electrode materials. The electrochemical parameters studied included five different electrode systems (Zr/Pt, Pd/Pt, C/Pt, Nb/Pt, and Ti/Pt), current densities (27.66, 55.33, …, 110.66 mA · cm−2) and pH values (3, 7, and 9) in 0.05 M sodium sulfate as supporting electrolyte. The electrical energy consumption and chemical oxygen demand were calculated for optimal conditions. The degradation efficiency was determined by high performance liquid chromatography (HPLC) equipped with a diode array detector, while the degradation products for both pesticides were identified and compared by ultra‐high performance liquid chromatography (UHPLC)‐mass spectrometry. The results could lead to an accurate estimate of their effect on the environment. A real water sample was used to study the influence of organic matter on pesticide degradation. Based on the results obtained the electrochemical treatment could be used for the successful removal of triketone herbicides from contaminated water.
Monte Carlo Simulations of the Phase Separation of a Copolymer Blend in a Thin Film
Authors: Wang Zhexiao , Shao Jing , Pan Heng , Feng Xiaoshuang , Chen Peng , Xia Ru , Wu Xiangsong , Qian Jiasheng
Published: December 2014

Monte Carlo simulations were carried out to study the phase separation of a copolymer blend comprising an alternating copolymer and/or block copolymer in a thin film, and a phase diagram was constructed with a series of composed recipes. The effects of composition and segregation strength on phase separation were discussed in detail. The chain conformation of the block copolymer and alternating copolymer were investigated with changes of the segregation strength. Our simulations revealed that the segment distribution along the copolymer chain and the segregation strength between coarse‐grained beads are two important parameters controlling phase separation and chain conformation in thin films of a copolymer blend. A well‐controlled phase separation in the copolymer blend can be used to fabricate novel nanostructures.
Preparation, Formation Mechanism, and Photoresponse Properties of GeSe Microtubes with a Rectangular Cross Section
Authors: Shi Liang , Li Yanan , Dai Yumei
Published: December 2014

GeSe single‐crystalline microtubes with a rectangular cross section have been fabricated through a facile solution approach. The as‐prepared GeSe microtubes have diameters in the range of 1–2 μm and wall thicknesses of approximately 100–200 nm. Crystal growth along the [010] direction is preferable for the GeSe microtubes. The formation of GeSe microtubes is proposed to originate from an etching effect of the solvent oleylamine. A clear photoresponsive behavior has been found for the as‐synthesized GeSe microtubes. The products were characterized by using powder XRD, energy‐dispersive X‐ray spectroscopy, TEM, SEM, and UV/Vis spectrophotometry.
Graphene oxide used as a surfactant to induce the flower‐like ZnO microstructures: growth mechanism and enhanced photocatalytic properties
Authors: Yao Chengli , Xie Anjian , Shen Yuhua , Zhu Weina , Zhu Jinmiao
Published: December 2014

In this paper, graphene oxide (GO) was used as a temple to induce the formation of flower‐like ZnO microparticals compared with surfactants, such as cetyltrimethylammonium bromide (CTAB) and dodecyl dimethyl betaine (BS‐12). The zinc hydroxide carbonate ((Zn4(CO3)(OH)6,ZHC)) was produced by a hydrothermal reaction. The flower‐like ZnO microparticals were gained by calcining ZHC. In the GO medium, the microparticals were assembled by numerous porous nanosheets from one point (initial nucleus) to flower‐like microparticals finally. The nanosheets of graphene oxide and functional groups were likely to contribute to the formation of the precursor, and some nanosheets were retained in the complex. The growth mechanism of ZHC was also proposed in this paper. The photocatalytic activity of the flower‐like ZnO microparticals was evaluated by photo degradation reaction of rhodamine B (RhB). The peony‐like porous ZnO/rGO compounds showed high photocatalytic activity and better than ZnO microparticals formed in the CTAB and BS‐12. These results indicated that GO could be widely used as a surfactant to induce composite materials with special morphology and photoelectric properties, etc.
Direct Alcohol Fuel Cells: Toward the Power Densities of Hydrogen‐Fed Proton Exchange Membrane Fuel Cells
Authors: Chen Yanxin , Bellini Marco , Bevilacqua Manuela , Fornasiero Paolo , Lavacchi Alessandro , Miller Hamish A. , Wang Lianqin , Vizza Francesco
Published: December 2014

A 2 μm thick layer of TiO2 nanotube arrays was prepared on the surface of the Ti fibers of a nonwoven web electrode. After it was doped with Pd nanoparticles (1.5 mgPd cm−2), this anode was employed in a direct alcohol fuel cell. Peak power densities of 210, 170, and 160 mW cm−2 at 80 °C were produced if the cell was fed with 10 wt % aqueous solutions of ethanol, ethylene glycol, and glycerol, respectively, in 2 M aqueous KOH. The Pd loading of the anode was increased to 6 mg cm−2 by combining four single electrodes to produce a maximum peak power density with ethanol at 80 °C of 335 mW cm−2. Such high power densities result from a combination of the open 3 D structure of the anode electrode and the high electrochemically active surface area of the Pd catalyst, which promote very fast kinetics for alcohol electro‐oxidation. The peak power and current densities obtained with ethanol at 80 °C approach the output of H2‐fed proton exchange membrane fuel cells.
Effects of neonatal fluoxetine exposure on behavior across development in rats selectively bred for an infantile affective trait
Authors: Zimmerberg Betty , Germeyan Sierra C.
Published: December 2014

Infants born to women with depressive symptoms are at higher risk for insecure attachment and behavioral problems. Thus current medical practice is to continue psychotropic medication of pregnant women with depression despite concerns about its behavioral teratology. There are few animal studies focused on long‐term behavioral effects of prenatal antidepressant exposure; in addition, studies have not looked at individual differences in baseline affective state as a source of response variability. In this study, fluoxetine, a selective serotonin reuptake inhibitor (SSRI), was administered to male and female rat pups from postnatal days 2–7 to model exposure to antidepressants in the human third trimester. Four behavioral measures were conducted from the neonatal to adult age periods in Low and High lines selectively bred for their rate of ultrasonic vocalizations after brief maternal separation. Neonatal fluoxetine administration decreased distress calls in both lines, but to a greater extent in High line rats than Low line. Neonatal fluoxetine also impaired motor coordination in neonates. Neonatal fluoxetine administration decreased social behavior in both juvenile and adult subjects. Fluoxetine‐related reductions in anxiety behavior were not observed at the two older ages. As expected, High line subjects displayed more anxiety behavior than Low line subjects at all three test ages. These results suggest that there are may be significant behavioral consequences of antidepressant use during late pregnancy on offspring maternal attachment and social behavior, with implications for increased risk of autism spectrum disorders. © 2014 Wiley Periodicals, Inc. Dev Psychobiol 57: 141–152, 2015.
Developmental insights into the pathology of and therapeutic strategies for DM1: Back to the basics
Authors: Chau Anthony , Kalsotra Auinash
Published: December 2014

Myotonic Dystrophy type 1 (DM1), the most prevalent adult onset muscular dystrophy, is a trinucleotide repeat expansion disease caused by CTG expansion in the 3′‐UTR of DMPK gene. This expansion results in the expression of toxic gain‐of‐function RNA that forms ribonuclear foci and disrupts normal activities of RNA‐binding proteins belonging to the MBNL and CELF families. Changes in alternative splicing, translation, localization, and mRNA stability due to sequestration of MBNL proteins and up‐regulation of CELF1 are key to DM1 pathology. However, recent discoveries indicate that pathogenic mechanisms of DM1 involves many other factors as well, including repeat associated translation, activation of PKC‐dependent signaling pathway, aberrant polyadenylation, and microRNA deregulation. Expression of the toxic repeat RNA culminates in the developmental remodeling of the transcriptome, which produces fetal isoforms of proteins that are unable to fulfill the physiological requirements of adult tissues. This review will describe advances in the understanding of DM1 pathogenesis as well as current therapeutic developments for DM1. Developmental Dynamics 244:377–390, 2015. © 2014 Wiley Periodicals, Inc.
IL‐33 activates eosinophils of visceral adipose tissue both directly and via innate lymphoid cells
Authors: Hashiguchi Masaaki , Kashiwakura Yuji , Kojima Hidefumi , Kobayashi Ayano , Kanno Yumiko , Kobata Tetsuji
Published: December 2014

Eosinophils are multifunctional leukocytes involved in allergic reactions as well as adipose tissue regulation. IL‐5 is required for eosinophil survival; however, the in vivo mechanisms of eosinophil regulation are not fully understood. A tg mouse model with il5 promoter‐driven EGFP expression was established for detecting the IL‐5‐producing cells in vivo. Il5‐egfp tg mice expressed high levels of EGFP in gonadal adipose tissue (GAT) cells. EGFP+ cells in GAT were mainly group 2 innate lymphoid cells (ILCs). IL‐33 preferentially expanded EGFP+ cells and eosinophils in GAT in vivo. EGFP+ ILCs were found to upregulate prg2 mRNA expression in GAT eosinophils. These results demonstrate that ILCs activate eosinophils in GAT. The blockage of IL‐33Rα, on the other hand, did not impair EGFP+ ILC numbers but did impair eosinophil numbers in vivo. GAT eosinophils expressed IL‐33Rα and IL‐33 expanded eosinophil numbers in CD90+ cell‐depleted mice. IL‐33 was further observed to induce the expression of retnla and epx mRNA in eosinophils. These findings demonstrate that IL‐33 directly activates eosinophils in GAT, and together with our other findings described above, our findings show that IL‐33 has dual pathways via which it activates eosinophils in vivo: a direct activation pathway and a group 2 ILC‐mediated pathway.
Inhibition of 4‐1BBL‐regulated TLR response in macrophages ameliorates endotoxin‐induced sepsis in mice
Authors: Bang Bo Ram , Kim Sang Jick , Yagita Hideo , Croft Michael , Kang Young Jun
Published: December 2014

Activation of Toll‐like receptor (TLR) signaling rapidly induces the expression of inflammatory genes, which is persistent for a defined period of time. However, uncontrolled and excessive inflammation may lead to the development of diseases. 4‐1BB ligand (4‐1BBL) plays an essential role in sustaining the expression of inflammatory cytokines by interacting with TLRs during macrophage activation. Here, we show that inhibition of 4‐1BBL signaling reduced the inflammatory responses in macrophages and ameliorated endotoxin‐induced sepsis in mice. A 4‐1BB‐Fc fusion protein significantly reduced TNF production in macrophages by blocking the oligomerization of TLR4 and 4‐1BBL. Administration of 4‐1BB‐Fc suppressed LPS‐induced sepsis by reducing TNF production, and the coadministration of anti‐TNF and 4‐1BB‐Fc provided better protection against LPS‐induced sepsis. Taken together, these observations suggest that inhibition of the TLR/4‐1BBL complex formation may be highly efficient in protecting against continued inflammation, and that 4‐1BB‐Fc could be a potential therapeutic target for the treatment of inflammatory diseases.
Designing Stable Radicals with Highly Electrophilic or Nucleophilic Character: Thiadiazinyl as a Case Study
Authors: De Vleeschouwer Freija , Chankisjijev Artiom , Geerlings Paul , De Proft Frank
Published: December 2014

Theoretical design can be an important aid in the discovery of valuable stable radical systems. In this study, inverse molecular design was applied to thiadiazinyl radicals to maximize two fundamental electronic properties in chemistry, namely electrophilicity and nucleophilicity. We discovered that the thiadiazinyl structure can be made moderately nucleophilic or highly electrophilic, depending on the electronic character of its substituents. The most electrophilic thiadiazinyl radical displays the highest electrophilic character encountered so far for uncharged radical systems. The accumulated data relating to the influence of different substituents at the various sites has allowed us to propose thiadiazinyl radicals that are intrinsically stable and as electrophilic or nucleophilic as possible. Although the nucleophilicity optimum fulfills the additional requirement of being stable, a significant drop from highly to merely moderately electrophilic is observed for the new electrophilicity optimum.
Applied Enantioselective Aminocatalysis: α‐Heteroatom Functionalization Reactions on the Carbapenem (β‐Lactam Antibiotic) Core
Authors: Cele Zamani E. D. , Arvidsson Per I. , Kruger Hendrik G. , Govender Thavendran , Naicker Tricia
Published: December 2014

The carbapenem (β‐lactam antibiotic) scaffold serves as a useful nucleophile in organocatalytic diarylprolinol trimethylsilyl ether mediated α‐heterofunctionalization reactions leading to the formation of diverse products that bear multiple stereocenters in high diastereoselectivity and moderate to good yields.
Voltammetric Determination of 8‐Nitroquinoline Using a Silver Solid Electrode and Its Application to Model Samples of Drinking and River Water
Authors: Rumlova Tereza , Barek Jiri , Matysik Frank‐Michael
Published: December 2014

This work is focused on the application of a silver solid electrode (AgE) for the development of modern voltammetric methods for the determination of submicromolar concentrations of biologically active compounds present in the environment. 8‐Nitroquinoline (8‐NQ), a well‐known chemical carcinogen, was chosen as a model substance. Differential pulse voltammetry (DPV) was used to study electrochemical behavior of 8‐NQ in different aqueous matrices. The following optimal conditions for determination of 8‐NQ in the concentration ranges from 2 to 100 µmol L−1 were used: BrittonRobinson (BR) buffer of pH 3.0, the regeneration potentials cycles (Ein=−1000 mV, Efin=−100 mV) and constant cleaning potential −2000 mV. Practical applicability of AgE for the determination of micromolar concentrations of 8‐NQ was verified on model samples of drinking and river water.
Current trends in the development of molecularly imprinted polymers in CEC
Authors: Mu Li‐Na , Wei Ze‐Hui , Liu Zhao‐Sheng
Published: December 2014

This review focused on the developments in the field of molecularly imprinted polymers (MIPs) for CEC since 2009. New preparation techniques of MIP‐based CEC, such as, portable microchip with macroporous monolithic imprinted microchannel, and low cross‐linking MIPs based on liquid crystalline monomers, were discussed. Using selected cases rather than a comprehensive review of the entire field, our goal is to highlight the studies of the interest with an emphasis on recent work, and offers suggestions for future development in the field of imprinted materials for CEC separation.
Equivalent peak resolution: Characterization of the extent of separation for two components based on their relative peak overlap
Authors: Dvořák Martin , Svobodová Jana , Dubský Pavel , Riesová Martina , Vigh Gyula , Gaš Bohuslav
Published: December 2014

Although the classical formula of peak resolution was derived to characterize the extent of separation only for Gaussian peaks of equal areas, it is often used even when the peaks follow non‐Gaussian distributions and/or have unequal areas. This practice can result in misleading information about the extent of separation in terms of the severity of peak overlap. We propose here the use of the equivalent peak resolution value, a term based on relative peak overlap, to characterize the extent of separation that had been achieved. The definition of equivalent peak resolution is not constrained either by the form(s) of the concentration distribution function(s) of the peaks (Gaussian or non‐Gaussian) or the relative area of the peaks. The equivalent peak resolution value and the classically defined peak resolution value are numerically identical when the separated peaks are Gaussian and have identical areas and SDs. Using our new freeware program, Resolution Analyzer, one can calculate both the classically defined and the equivalent peak resolution values. With the help of this tool, we demonstrate here that the classical peak resolution values mischaracterize the extent of peak overlap even when the peaks are Gaussian but have different areas. We show that under ideal conditions of the separation process, the relative peak overlap value is easily accessible by fitting the overall peak profile as the sum of two Gaussian functions. The applicability of the new approach is demonstrated on real separations.
The relation between social network site usage and loneliness and mental health in community‐dwelling older adults
Authors: Aarts S. , Peek S. T. M. , Wouters E. J. M.
Published: December 2014

Background

Loneliness is expected to become an even bigger social problem in the upcoming decades, because of the growing number of older adults. It has been argued that the use of social network sites can aid in decreasing loneliness and improving mental health. The purpose of this study was to examine whether and how social network sites usage is related to loneliness and mental health in community‐dwelling older adults.

Method

The study population included community‐dwelling older adults aged 60 and over residing in the Netherlands (n = 626) collected through the LISS panel (www.lissdata.nl). Univariate and multivariate linear regression analyses, adjusted for potentially important confounders, were conducted in order to investigate the relation between social network sites usage and (emotional and social) loneliness and mental health.

Results

More than half of the individuals (56.2%) reported to use social network sites at least several times per week. Social network sites usage appeared unrelated to loneliness in general, and to emotional and social loneliness in particular. Social network sites usage also appeared unrelated to mental health. Several significant associations between related factors and the outcomes at hand were detected.

Conclusion

In this sample, which was representative for the Dutch population, social network sites usage was unrelated to loneliness and/or mental health. The results indicate that a simple association between social network site usage and loneliness and mental health as such, cannot automatically be assumed in community‐dwelling older adults. Copyright © 2014 John Wiley & Sons, Ltd.
Above‐moderate physical activity reduces both incident and persistent late‐life depression in rural Koreans
Authors: Park Jee Eun , Lee Jun‐Young , Kim Byung‐Soo , Kim Ki Woong , Chae Song Hwa , Cho Maeng Je
Published: December 2014

Objective

To investigate the natural course of depressive symptoms among community‐dwelling elderly over 5 years. Rates and correlates of the incidence and the persistence of late‐life depression were examined.

Methods

A total of 701 elderly people 65 years of age or older without dementia at baseline were included in this study. The association between categorically defined late‐life depression (score of ≥8 on the Korean version of the Geriatric Depression Scale‐Short Form) and possible lifestyle and clinical risk factors, including physical activity assessed with a modified Korean version of the International Physical Activity Questionnaire (IPAQ) and transformed into weekly Metabolic Equivalent Task (MET) values, was longitudinally investigated using multiple logistic regression analyses. Adjustment was done with sociodemographic variables, chronic medical illnesses, and cognitive dysfunction.

Results

During the 5‐year follow‐up, 74 (26.5%) of the non‐depressed elderly developed depression, whereas 30 (49.2%) of the depressed elderly experienced persistent depression. Above‐moderate baseline physical activity was independently associated with decreased incidence and persistence rates of late‐life depression (adjusted odds ratio (AOR) = 0.44, 95% confidence interval (CI) = 0.22–0.85; AOR = 0.17, 95% CI = 0.03–0.92, respectively), whereas mild physical activity was not. Conversely, poorer executive function also predicted 5‐year incident depression (AOR = 0.93, 95% CI = 0.89–0.98) but not persistent depression.

Conclusion

This study suggests that a minimum of moderate physical activity is related to both emergent and persistent depression in elderly individuals. Research with an extended follow‐up period and a shorter inter‐assessment interval is needed to confirm this result. Copyright © 2014 John Wiley & Sons, Ltd.
Exploring spatiotemporal network transitions in task functional MRI
Authors: Scott Gregory , Hellyer Peter J. , Hampshire Adam , Leech Robert
Published: December 2014

A critical question for cognitive neuroscience regards how transitions between cognitive states emerge from the dynamic activity of functional brain networks. Here we combine a simple data reorganization with spatial independent component analysis (ICA), enabling a spatiotemporal ICA (stICA) which captures the consistent evolution of networks during the onset and offset of a task. The technique was applied to functional magnetic resonance imaging (MRI) (FMRI) datasets involving alternating between rest and task, and to simple synthetic data. Starting and finishing time‐points of periods of interest (anchors) were defined at task block onsets and offsets. For each subject, the 10 volumes following each anchor were extracted and concatenated spatially, producing a single 3D sample. Samples for all anchors and subjects were concatenated along the fourth dimension. This 4D dataset was decomposed using ICA into spatiotemporal components. One component exhibited the transition with task onset from a default mode network (DMN) becoming less active to a frontoparietal control network becoming more active. We observed other changes with relevance to understanding network dynamics, for example, the DMN showed a changing spatial distribution, shifting to an anterior/superior pattern of deactivation during task from a posterior/inferior pattern during rest. By anchoring analyses to periods associated with the onsets and offsets of task, our approach reveals novel aspects of the dynamics of network activity accompanying these transitions. Importantly, these findings were observed without specifying a priori either the spatial networks or the task time courses. Hum Brain Mapp 36:1348–1364, 2015. © 2014 Wiley Periodicals, Inc.
Thalamic involvement in paroxysmal kinesigenic dyskinesia: A combined structural and diffusion tensor MRI analysis
Authors: Kim Ji Hyun , Kim Dong‐Wook , Kim Jung Bin , Suh Sang‐il , Koh Seong‐Beom
Published: December 2014

Alteration of basal ganglia‐thalamocortical circuit has been hypothesized to play a role in the pathophysiology underlying paroxysmal kinesigenic dyskinesia (PKD). We investigated macrostructural and microstructural changes in PKD patients using structural and diffusion tensor magnetic resonance imaging (MRI) analyses. Twenty‐five patients with idiopathic PKD and 25 control subjects were prospectively studied on a 3T magnetic resonance (MR) scanner. Cortical thickness analysis was used to evaluate cortical gray matter (GM) changes, and automated volumetry and shape analysis were used to assess volume changes and shape deformation of the subcortical GM structures, respectively. Tract‐based spatial statistics (TBSS) was used to evaluate white matter integrity changes in a whole‐brain manner, and region‐of‐interest (ROI) analysis of diffusion tensor metrics was performed in subcortical GM structures. Compared to controls, PKD patients exhibited a reduction in volume of bilateral thalami and regional shape deformation mainly localized to the anterior and medial aspects of bilateral thalami. TBSS revealed an increase in fractional anisotropy (FA) of bilateral thalami and right anterior thalamic radiation in patients relative to controls. ROI analysis also showed an increase in FA of bilateral thalami in patients compared to controls. We have shown evidence for thalamic abnormalities of volume reduction, regional shape deformation, and increased FA in patients with PKD. Our novel findings of concomitant macrostructural and microstructural abnormalities in the thalamus lend further support to previous observations indicating causal relationship between a preferential lesion in the thalamus and development of PKD, thus providing neuroanatomical basis for the involvement of thalamus within the basal ganglia‐thalamocortical pathway in PKD. Hum Brain Mapp 36:1429–1441, 2015. © 2014 Wiley Periodicals, Inc.
Adverse and Advantageous Selection in the Medicare Supplemental Market: A Bayesian Analysis of Prescription drug Expenditure
Authors: Li Qian , Trivedi Pravin K.
Published: December 2014

This paper develops an extended specification of the two‐part model, which controls for unobservable self‐selection and heterogeneity of health insurance, and analyzes the impact of Medicare supplemental plans on the prescription drug expenditure of the elderly, using a linked data set based on the Medicare Current Beneficiary Survey data for 2003–2004. The econometric analysis is conducted using a Bayesian econometric framework. We estimate the treatment effects for different counterfactuals and find significant evidence of endogeneity in plan choice and the presence of both adverse and advantageous selections in the supplemental insurance market. The average incentive effect is estimated to be $757 (2004 value) or 41% increase per person per year for the elderly enrolled in supplemental plans with drug coverage against the Medicare fee‐for‐service counterfactual and is $350 or 21% against the supplemental plans without drug coverage counterfactual. The incentive effect varies by different sources of drug coverage: highest for employer‐sponsored insurance plans, followed by Medigap and managed medicare plans. Copyright © 2014 John Wiley & Sons, Ltd.