bluuebunny/crossref_metadata_2025 huggingface dataset:
Tridentate Lewis Acids Based on 1,3,5‐Trisilacyclohexane Backbones and an Example of Their Host–Guest Chemistry
Authors: Weisheim Eugen , Reuter Christian G. , Heinrichs Peter , Vishnevskiy Yury V. , Mix Andreas , Neumann Beate , Stammler Hans‐Georg , Mitzel Norbert W.
Published: July 2015

Directed tridentate Lewis acids based on the 1,3,5‐trisilacyclohexane skeleton with three ethynyl groups [CH2Si(Me)(C2H)]3 were synthesised and functionalised by hydroboration with HB(C6F5)2, yielding the ethenylborane {CH2Si(Me)[C2H2B(C6F5)2]}3, and by metalation with gallium and indium organyls affording {CH2Si(Me)[C2M(R)2]}3 (M=Ga, In, R=Me, Et). In the synthesis of the backbone the influence of substituents (MeO, EtO and iPrO groups at Si) on the orientation of the methyl group was studied with the aim to increase the abundance of the all‐cis isomer. New compounds were identified by elemental analyses, multi‐nuclear NMR spectroscopy and in some cases by IR spectroscopy. Crystal structures were obtained for cis‐trans‐[CH2Si(Me)(Cl)]3, all‐cis‐[CH2Si(Me)(H)]3, all‐cis‐[CH2Si(Me)(C2H)]3, cis‐trans‐[CH2Si(Me)(C2H)]3 and all‐cis‐[CH2Si(Me)(C2SiMe3)]3. A gas‐phase electron diffraction experiment for all‐cis‐[CH2Si(Me)(C2H)]3 provides information on the relative stabilities of the all‐equatorial and all‐axial form; the first is preferred in both solid and gas phase. The gallium‐based Lewis acid {CH2Si(Me)[C2Ga(Et)2]}3 was reacted with a tridentate Lewis base (1,3,5‐trimethyl‐1,3,5‐triazacyclohexane) in an NMR titration experiment. The generated host–guest complexes involved in the equilibria during this reaction were identified by DOSY NMR spectroscopy by comparing measured diffusion coefficients with those of the suitable reference compounds of same size and shape.
Palladium‐Catalyzed Arylation of (Di)azinyl Aldoxime Ethers by Aryl Iodides: Stereoselective Synthesis of Unsymmetrical (E)‐(Di)azinylaryl Ketoxime Ethers
Authors: Gou Quan , Deng Bin , Qin Jun
Published: July 2015

The first example of direct arylation of (di)azinyl aldoxime ethers by aryl iodides is reported. The reaction produces, in a single step, a variety of geometrically pure unsymmetrical (E)‐(di)azinylaryl ketoxime ethers, a class of nitrogenated motifs that have found wide applications in medicinal and organic chemistry but are difficult to access using conventional procedure. The utility of the method is further illustrated in a formal synthesis of the Merck melanin‐concentrating hormone 1 receptor antagonist.
Surface‐Assisted Cyclodehydrogenation; Break the Symmetry, Enhance the Selectivity
Authors: Wiengarten Alissa , Lloyd Julian A. , Seufert Knud , Reichert Joachim , Auwärter Willi , Han Runyuan , Duncan David A. , Allegretti Francesco , Fischer Sybille , Oh Seung Cheol , Sağlam Özge , Jiang Li , Vijayaraghavan Saranyan , Écija David , Papageorgiou Anthoula C. , Barth Johannes V.
Published: July 2015

Selectivity in chemical reactions is a major objective in industrial processes to minimize spurious byproducts and to save scarce resources. In homogeneous catalysis the most important factor which determines selectivity is structural symmetry. However, a transfer of the symmetry concept to heterogeneous catalysis still requires a detailed comprehension of the underlying processes. Here, we investigate a ring‐closing reaction in surface‐confined meso‐substituted porphyrin molecules by scanning tunneling microscopy, temperature‐programmed desorption, and computational modeling. The identification of reaction intermediates enables us to analyze the reaction pathway and to conclude that the symmetry of the porphyrin core is of pivotal importance regarding product yields.
Selective Alkylation of C‐Rich Bulge Motifs in Nucleic Acids by Quinone Methide Derivatives
Authors: Lönnberg Tuomas , Hutchinson Mark , Rokita Steven
Published: July 2015

A quinone methide precursor featuring a bis‐cyclen anchoring moiety has been synthesized and its capacity to alkylate oligonucleotide targets quantified in the presence and absence of divalent metal ions (Zn2+, Ni2+ and Cd2+). The oligonucleotides were designed for testing the sequence and secondary structure specificity of the reaction. Gel electrophoretic analysis revealed predominant alkylation of C‐rich bulges, regardless of the presence of divalent metal ions or even the bis‐cyclen anchor. This C‐selectivity appears to be an intrinsic property of the quinone methide electrophile as reflected by its reaction with an equimolar mixture of the 2′‐deoxynucleosides. Only dA‐N1 and dC‐N3 alkylation products were detected initially and only the dC adduct persisted for detection under conditions of the gel electrophoretic analysis.
ChemInform Abstract: Novel Environment Friendly Inorganic Red Pigments Based on Bi4V2O11.
Authors: Wendusu Wendusu , Shiraishi Atsunori , Takeuchi Naoki , Masui Toshiyuki , Imanaka Nobuhito
Published: July 2015

(Bi1‐x‐yZrxAly) 4V2O11+δ (x = 0‐0.15; y = 0‐0.10) ceramic pigments are prepared by calcination of stoichiometric amounts of Bi2O3, ZrO2, Al2O3, and V2O5 in air or O2 (800 °C, 10 h).
ChemInform Abstract: Synthesis and Characterization of PbBaGeO4.
Authors: Petschnig Lucas L. , Huppertz Hubert
Published: July 2015

The novel title compound is prepared by solid state reaction of stoichiometric amounts of PbO, BaCO3, and GeO2 (Pt crucible, 900 °C, 2 d).
ChemInform Abstract: Polyoxometalate‐Based Nickel Clusters as Visible Light‐Driven Water Oxidation Catalysts.
Authors: Han Xin‐Bao , Li Yang‐Guang , Zhang Zhi‐Ming , Tan Hua‐Qiao , Lu Ying , Wang En‐Bo
Published: July 2015

The new polyoxometalate(POM)‐based polynuclear cluster compounds (V), (VI), and (VII) contain {Ni12}, {Ni13}, and {Ni25} cores, resp., connected by hydroxide, phosphate, and (for V and VII) carbonate linkers and encapsulated by lacunary A‐α‐{SiW9O34} POM units.
ChemInform Abstract: Synthesis, Structure, Multiband Optical, and Electrical Conductive Properties of a 3D Open Cubic Framework Based on [Cu8Sn6S24]z‐ Clusters.
Authors: Zhang Xian , Wang Qiuran , Ma Zhimin , He Jianqiao , Wang Zhe , Zheng Chong , Lin Jianhua , Huang Fuqiang
Published: July 2015

Compounds (IV) and (VI) are synthesized using thiourea as a flux and by a hydrothermal method, respectively.
ChemInform Abstract: Ferrocene‐Based Planar Chiral Imidazopyridinium Salts for Catalysis.
Authors: Check Christopher T. , Jang Ki Po , Schwamb C. Benjamin , Wong Alexander S. , Wang Michael H. , Scheidt Karl A.
Published: July 2015

Novel enantiopure planar, chiral ferrocenyl imidazolium complexes are presented.
ChemInform Abstract: Chemo‐ and Stereoselective Synthesis of Fluorinated Enamides from Ynamides in HF/Pyridine: Second‐Generation Approach to Potent Ureas Bioisosteres.
Authors: Metayer Benoit , Compain Guillaume , Jouvin Kevin , Martin‐Mingot Agnes , Bachmann Christian , Marrot Jerome , Evano Gwilherm , Thibaudeau Sebastien
Published: July 2015

The corresponding mixtures of E and Z isomers can be easily separated by flash chromatography.
ChemInform Abstract: Organoaluminum‐Mediated Direct Cross‐Coupling Reactions.
Authors: Minami Hiroki , Saito Tatsuo , Wang Chao , Uchiyama Masanobu
Published: July 2015

A direct cross‐coupling reaction between arylaluminum compounds and organic halides is presented.
ChemInform Abstract: Copper(I)‐Catalyzed Alkylation of Polyfluoroarenes Through Direct C—H Bond Functionalization.
Authors: Xu Shuai , Wu Guojiao , Ye Fei , Wang Xi , Li Huan , Zhao Xia , Zhang Yan , Wang Jianbo
Published: July 2015

A copper(I)‐catalyzed alkylation of polyfluoroarenes with N‐tosylhydrazones or diazo compounds is developed.
ChemInform Abstract: Synthesis of Bis‐spiro Cyclopropanes Based on Meldrum′s Acid by Milling.
Authors: Kashani Elmira , Noroozi Pesyan Nader , Tunc Tuncay , Sahin Ertan
Published: July 2015

Reaction of Meldrum′s acid with various solid aldehydes in the presence of cyanogen bromide and solid sodium ethoxide leads to the selective and efficient formation of bis‐spiro cyclopropanes (III) under mild conditions.
ChemInform Abstract: A Sustainable and Simple Catalytic System for Direct Alkynylation of C(sp2)—H Bonds with Low Nickel Loadings.
Authors: Liu Yue‐Jin , Liu Yan‐Hua , Yan Sheng‐Yi , Shi Bing‐Feng
Published: July 2015

The direct alkynylation of unactivated aryl C—H bonds employing a removable auxiliary requires only low nickel loadings (0.5 mol%).
ChemInform Abstract: One‐Pot Synthesis of O‐Allylhydroxylamines Through the Organocatalytic Oxidation of Tertiary Allylic Amines Followed by a [2,3]‐Meisenheimer Rearrangement.
Authors: Theodorou Alexis , Limnios Dimitris , Kokotos Christoforos G.
Published: July 2015

The title reaction offers a cheap and efficient synthesis of the title compounds.
ChemInform Abstract: Disulfonimide‐Catalyzed Asymmetric Synthesis of δ‐Amino‐β‐Keto Esters.
Authors: Wang Qinggang , List Benjamin
Published: July 2015

The title compounds (III) are obtained by vinylogous Mukaiyama‐Mannich reaction of the Chan diene (II) with various Boc‐protected imines (I) catalyzed by a chiral disulfonimide.
ChemInform Abstract: Copper‐Mediated ortho C—H Sulfonylation of Benzoic Acid Derivatives with Sodium Sulfinates.
Authors: Liu Jidan , Yu Lin , Zhuang Shaobo , Gui Qingwen , Chen Xiang , Wang Wenduo , Tan Ze
Published: July 2015

A novel copper‐mediated auxiliary‐assisted ortho C—H bond sulfonylation of the benzoic acid derivative with a variety of sodium sulfinates is reported.
ChemInform Abstract: PhI(OCOCF3)2‐Catalyzed Nucleophilic Substitution of Aromatic Propargyl Alcohols.
Authors: Weng Shiue‐Shien , Hsieh Kun‐Yi , Zeng Zih‐Jian
Published: July 2015

According to the title reaction, a variety of terminal, 3‐aryl, 3‐alkyl, and 3‐silyl substituted propargyl alcohols are transformed with various nucleophiles.
ChemInform Abstract: Preparation of (Substituted) Picenes via Solar Light‐Induced Mallory Photocyclization.
Authors: Protti Stefano , Artioli Gianluca A. , Capitani Francesco , Marini Carlo , Dore Paolo , Postorino Paolo , Malavasi Lorenzo , Fagnoni Maurizio
Published: July 2015

Picenes (II) are easily obtained by the title reaction.
ChemInform Abstract: Expedient Approach for the Synthesis of Trispiropyrrolidine Bisoxindoles Through 1,3‐Dipolar Cycloaddition Reactions.
Authors: Feng Guo‐Liang , Li Yue , Geng Li‐Jun , Zhang Hong‐Li , Shi Yan‐Jing , Wang Kai‐Fang
Published: July 2015

13 Title compounds (IV) are prepared by a regio‐ and stereoselective three‐component reaction.
ChemInform Abstract: Copper‐Catalyzed 1,3‐Dipolar Cycloaddition of Methyleneindolinones and N,N′‐Cyclic Azomethine Imines.
Authors: Zhang Di , Zhang Da‐Ming , Xu Guang‐Yang , Sun Jiang‐Tao
Published: July 2015

The reaction furnishes N‐Cbz‐protected spiro[pyrazolidin‐3,3′‐oxindoles] in high yields and with high diastereoselectivity.
ChemInform Abstract: The Design, Synthesis and Application of Imidazolium‐Tagged Ferrocenyl Oxazoline Phosphine Ligands for the Asymmetric 1,3‐Dipolar Cycloaddition of Azomethine Ylides with Nitroalkenes: Ion Effect for Enhancing the Reactivity, Stereoselectivity and Recyclability.
Authors: Dai Li , Xu Di , Dong Xiao , Zhou Zhiming
Published: July 2015

A series of chiral ferrocenyl oxazoline phosphine ligands is prepared one of which proves valuable for the preparation of substituted pyrrolidine derivatives in high yields, with high to excellent diastereoselectivities and excellent enantioselectivities.
ChemInform Abstract: Broensted Acid Catalyzed α′‐Functionalization of Silylenol Ethers with Indoles.
Authors: Ayala Caitlan E. , Dange Nitin S. , Fronczek Frank R. , Kartika Rendy
Published: July 2015

Pyridinium triflate catalyzes the highly regioselective carbon—carbon bond formation between indoles and silylenol ethers.
ChemInform Abstract: Catalytic Aerobic Oxidation and Tandem Enantioselective Cycloaddition in Cascade Multicomponent Synthesis.
Authors: Potowski Marco , Merten Christian , Antonchick Andrey P. , Waldmann Herbert
Published: July 2015

Copper catalyzed aerobic oxidation of cyclopentadiene to cyclopentadienone and subsequent asymmetric 1,3‐dipolar cycloaddition of azomethine ylides produces tricyclic ketones with excellent diastereo‐ and enantioselectivities.
ChemInform Abstract: Clean and Efficient Synthesis of Pyrazole Derivatives in Aqueous Media
Authors: Xu Pan , Xi Yu‐Kun , Chen Hui , Shi Da‐Qing
Published: July 2015

via reaction of 3‐amino‐1‐arylpropenones (I) with hydrazines without using any catalyst
ChemInform Abstract: The Synthesis of Some Fused Pyrazolo‐1,4‐naphthoquinones
Authors: Molinari Aurora , Oliva Alfonso , Arismendi Marlene , Imbarack Elizabeth , Galvez Cristian , Maldonado Javier , Feliciano Arturo San
Published: July 2015

and related isoxazolonaphthoquinone (IV) via reaction of 2‐acetylnaphthoquinone (I) with hydrazines and hydroxylamine, respectively
ChemInform Abstract: CuFeO4 Nanoparticles: An Efficient Heterogeneous Magnetically Separable Catalyst for Synthesis of Some Novel Propynyl‐1H‐Imidazoles Derivatives.
Authors: El‐Remaily Mahmoud Abd El Aleem , Abu‐Dief Ahmed M.
Published: July 2015

The catalyst is reused in six catalytic cycles without significant loss of its activity.
ChemInform Abstract: Regioselective Three‐Component Reactions of Enaminones, 2‐Aminopyridines and Enals for the Synthesis of 1,2‐Dihydropyridines.
Authors: Cao Shuo , Xin Luoting , Liu Yunyun , Wan Jie‐Ping , Wen Chengping
Published: July 2015

Title compounds (IV) are easily and regioselectively synthesized using cheap catalysts.
ChemInform Abstract: A Synthesis of 4‐Aryl Quinolin‐2(1H)‐ones by Acidic Zeolite Promoted Intramolecular Cyclization of N‐Aryl Amides of 3‐Arylpropynoic Acids.
Authors: Ryabukhin Dmitry S. , Vasilyev Aleksander V.
Published: July 2015

The novel method provides a variety of quinoline derivatives in high yields.
ChemInform Abstract: Asymmetric Ruthenium‐Catalyzed Hydrogenation of 2,6‐Disubstituted 1,5‐Naphthyridines: Access to Chiral 1,5‐Diaza‐cis‐Decalins.
Authors: Zhang Jianwei , Chen Fei , He Yan‐Mei , Fan Qing‐Hua
Published: July 2015

The first enantioselective hydrogenation of 1,5‐naphthyridines, catalyzed by chiral cationic ruthenium diamine complexes, is developed.
ChemInform Abstract: Expedient Copper‐Catalyzed Borylation Reactions Using Amino Acids as Ligands.
Authors: Liu Meng‐Yan , Hong Shi‐Bin , Zhang Wei , Deng Wei
Published: July 2015

Conditions for the borylation of primary and secondary alkyl bromides equipped with various functional groups using dipinacolyl hypodiborate (II) or bis(neopentylglycolato)diboron (IV) are elaborated.
ChemInform Abstract: Regio‐ and Steroselective Cross‐Metathesis of Silylacetylenes with Terminal Olefins and α,ω‐Dienes.
Authors: Ostrowska Sylwia , Powala Beata , Jankowska‐Wajda Magdalena , Zak Patrycja , Rogalski Szymon , Wyrzykiewicz Bozena , Pietraszuk Cezary
Published: July 2015

2‐Silyl‐1,3‐dienes (III) and 2‐silyl‐1,3,n‐trienes (V) are efficiently obtained with complete E‐selectivity.
ChemInform Abstract: A New Triterpenoid and Potential Anticancer Cytotoxic Activity of Isolated Compounds from the Roots of Eucalyptus citriodora.
Authors: He Ying , Shang Qisong , Tian Liping
Published: July 2015

A new triterpenoid, citriodora A (I), is isolated along with five known compounds.
ChemInform Abstract: Thermodynamic Properties of Alkalis Borates
Authors: Zhang Sisi , Lin Chenxiao , Guo Yafei , Wang Shiqiang , Deng Tianlong
Published: July 2015

Review: 30 refs.
ChemInform Abstract: Understanding Ferroelectricity in Layered Perovskites: New Ideas and Insights from Theory and Experiments
Authors: Benedek Nicole A. , Rondinelli James M. , Djani Hania , Ghosez Philippe , Lightfoot Philip
Published: July 2015

Review: 160 refs.
ChemInform Abstract: Sorption of Radionuclides from Aqueous Systems onto Graphene Oxide‐Based Materials: A Review
Authors: Yu Shujun , Wang Xiangxue , Tan Xiaoli , Wang Xiangke
Published: July 2015

Review: 212 refs.
ChemInform Abstract: Role of Anions Associated with the Formation and Properties of Silver Clusters
Authors: Wang Quan‐Ming , Lin Yu‐Mei , Liu Kuan‐Guan
Published: July 2015

Review: 40 refs.
ChemInform Abstract: Uranium Triamidoamine Chemistry
Authors: Gardner Benedict M. , Liddle Stephen T.
Published: July 2015

Review: [57 refs.
ChemInform Abstract: Electrophilic Amination: The Case of Nitrenoids
Authors: Starkov Pavel , Jamison Timothy F. , Marek Ilan
Published: July 2015

Review: [discovery, structural features and chemical reactivity of nitrenoids; advances in applying nitrenoids as well as current limitations and future directions; 95 refs.
ChemInform Abstract: Ionic Liquid‐Stabilized Nanoparticles as Catalysts for the Conversion of Biomass
Authors: Luska K. L. , Migowski P. , Leitner W.
Published: July 2015

Review: 102 refs.
ChemInform Abstract: Development of Novel Cyclizations via Rhodacycle Intermediate and Its Application to Synthetic Organic Chemistry
Authors: Oonishi Yoshihiro
Published: July 2015

Review: 64 refs.
ChemInform Abstract: Phthalazin‐1(2H)‐one as a Remarkable Scaffold in Drug Discovery
Authors: Vila Noemi , Besada Pedro , Costas Tamara , Costas‐Lago M. Carmen , Teran Carmen
Published: July 2015

Review: [137 refs.
ChemInform Abstract: Recent Advances in Iron‐Catalyzed C(sp2)—C(sp2) Cross‐Couplings
Authors: Kuzmina Olesya M. , Steib Andreas K. , Moyeux Alban , Cahiez Gerard , Knochel Paul
Published: July 2015

Review: [44 refs.
ChemInform Abstract: Bioactive Heterocycles Containing Endocyclic N‐Hydroxy Groups
Authors: Rani Reshma , Granchi Carlotta
Published: July 2015

Review: 159 refs.
ChemInform Abstract: Biologically Active Compounds Based on the Privileged 2‐Imidazoline Scaffold: The World Beyond Adrenergic/Imidazoline Receptor Modulators
Authors: Krasavin Mikhail
Published: July 2015

Review: 81 refs.
ChemInform Abstract: In Search of Uracil Derivatives as Bioactive Agents. Uracils and Fused Uracils: Synthesis, Biological Activity and Applications
Authors: Palasz Aleksandra , Ciez Dariusz
Published: July 2015

Review: [71 refs.
ChemInform Abstract: N‐Bridged 5,6‐Bicyclic Pyridines: Recent Applications in Central Nervous System Disorders
Authors: Delgado Oscar , Delgado Francisca , Vega Juan Antonio , Trabanco Andres A.
Published: July 2015

Review: [81 refs.
ChemInform Abstract: Chemical Principles Underpinning the Performance of the Metal—Organic Framework HKUST‐1
Authors: Hendon Christopher H. , Walsh Aron
Published: July 2015

Review: 117 refs.
ChemInform Abstract: Kinetic Monte Carlo Simulation of Statistical Mechanical Models and Coarse‐Grained Mesoscale Descriptions of Catalytic Reaction‐Diffusion Processes: 1D Nanoporous and 2D Surface Systems
Authors: Liu Da‐Jiang , Garcia Andres , Wang Jing , Ackerman David M. , Wang Chi‐Jen , Evans James W.
Published: July 2015

Review: 314 refs.
Modulare chemische Reaktoren für die Prozessentwicklung und Produktion in kontinuierlichen Mehrzweckanlagen
Authors: Kockmann Norbert
Published: July 2015

Kleinskalige, kontinuierlich betriebene Prozesse sind ein aktuelles Forschungsgebiet in der chemischen Industrie zur schnellen Prozessentwicklung und Produktion kleiner Mengen. Der Beitrag beschreibt ein Baukastensystem für kontinuierlich betriebene chemische Reaktoren bestehend aus Chip‐ oder Platten‐Reaktoren zum schnellen Vermischen, Kapillar‐ oder Wendelrohrreaktoren zur definierten Einstellung der Verweilzeit sowie kontinuierlich betriebene Rührkessel. Die beteiligten Phasen des chemischen Systems bestimmen die eingesetzten Bausteine oder Module und ermöglichen damit eine flexible Mehrzweck‐Anlage.
Theoretical Study of Electronic Structures and Charge Transport Properties of 9,10‐Bis((E)‐2‐(pyrid‐n‐yl) vinyl) (n=2,3,4) Anthracene
Authors: Guo Qing , Wang Lijuan , Jiang Yuanfei , Guo Jing , Xu Bin , Tian Wenjing
Published: July 2015

Charge carrier mobility is one of the most significant properties for organic semiconductors. In this work, the electronic structures and charge transport properties of 9,10‐bis((E)‐2‐(pyrid‐n‐yl)vinyl) (n=2, 3, 4) anthracene (BP2VA, BP3VA and BP4VA) were investigatedviathe analysis of the molecular geometry, the reorganization energy, the frontier orbital and density of state, as well as the electronic coupling and the charge mobility. The results indicated that the linkage between 9,10‐divinyl anthracene unit and pyridine (ortho‐,meta‐andpara‐) influenced not only the intra‐molecular conformation (i.e., the reorganization energies), but also the intermolecular interaction (i.e., transfer integrals), and finally the charge mobility of the molecules. It is also found that: (1) The calculated charge mobilties of holes are dozens of times higher than those of electrons for the three molecules. (2) The charge mobilities of hole and electron of the three molecules display the trend:μBP4VA>μBP2VA>μBP3VA, and the hole mobility of BP4VA is as high as ~1 cm2/(V·s).
Enhancing the Structural Diversity and Bioactivity of Natural Products by Combinatorial Modification Exemplified by Total Tanshinones
Authors: Tan Yafang , Sun Xiaohui , Dong Fuyue , Tian Haiyan , Jiang Renwang
Published: July 2015

To enhance the structural diversity of tanshinones and provide more derivatives for the biological studies, a one‐pot combinatorial modification strategy was performed on total tanshinones. Six new quinoxlinetanshinones 1–6 were subsequently isolated from the combinatorial modified semi‐synthetic mixture. The structures were elucidated by spectroscopic analysis in combination with single‐crystal X‐ray diffraction. These quinoxlinetanshinones demonstrated strong DNA binding properties. Rapid synthesis of new quinoxlinetanshinones with significant biological activity highlights the great potential of one‐pot combinatorial modification for the diversification of natural products.
Cognitive and Physical Function by Statin Exposure in Elderly Individuals Following Acute Myocardial Infarction
Authors: Swiger Kristopher J. , Martin Seth S. , Tang Fengming , Blaha Michael J. , Blumenthal Roger S. , Alexander Karen P. , Arnold Suzanne V. , Spertus John A.
Published: July 2015

Despite beneficial effects on morbidity and mortality after acute myocardial infarction (AMI), concerns remain about the safety of statin therapy, particularly their potential effects on cognitive and physical function, in elderly individuals. Among statin‐naive AMI patients age ≥65 years in a multicenter US registry, we examined the association between statin prescription at discharge and change in cognition (via Modified Telephone Interview for Cognitive Status [TICS‐M]) assessed at 1 and 6 months after AMI. Short Form‐12 Physical Component score, hand grip, walk time, and chair‐rise tests were used to assess physical function. We conducted noninferiority testing to evaluate the hypothesis that the mean change in cognitive function was no worse among patients recently started on statins compared with those who were not. Among 317 elderly AMI patients, 262 patients (83%) were prescribed a statin at discharge and 55 were not. After matching for propensity to be discharged on statin after AMI, the effect of statin treatment on change in TICS‐M from 1 to 6 months (estimated difference, 0.11 points; 95% confidence interval: −2.11 to 2.32, P = 0.92) showed noninferiority (inferiority threshold 3 points). There were no significant differences in any physical function measure. Among statin‐naive elderly individuals recovering from AMI, initiation of statin therapy was not associated with detectable changes in short‐term cognitive or physical function. These findings support the general safety of statin therapy for secondary prevention in this population.
Predicting Molecular Targets for Small‐Molecule Drugs with a Ligand‐Based Interaction Fingerprint Approach
Authors: Cao Ran , Wang Yanli
Published: July 2015

The computational prediction of molecular targets for small‐molecule drugs remains a great challenge. Herein we describe a ligand‐based interaction fingerprint (LIFt) approach for target prediction. Together with physics‐based docking and sampling methods, we assessed the performance systematically by modeling the polypharmacology of 12 kinase inhibitors in three stages. First, we examined the capacity of this approach to differentiate true targets from false targets with the promiscuous binder staurosporine, based on native complex structures. Second, we performed large‐scale profiling of kinase selectivity on the clinical drug sunitinib by means of computational simulation. Third, we extended the study beyond kinases by modeling the cross‐inhibition of bromodomain‐containing protein 4 (BRD4) for 10 well‐established kinase inhibitors. On this basis, we made prospective predictions by exploring new kinase targets for the anticancer drug candidate TN‐16, originally known as a colchicine site binder and microtubule disruptor. As a result, p38α was highlighted from a panel of 187 different kinases. Encouragingly, our prediction was validated by an in vitro kinase assay, which showed TN‐16 as a low‐micromolar p38α inhibitor. Collectively, our results suggest the promise of the LIFt approach in predicting potential targets for small‐molecule drugs.
Concurrency in electrical neuroinformatics: parallel computation for studying the volume conduction of brain electrical fields in human head tissues
Authors: Salman Adnan , Malony Allen , Turovets Sergei , Volkov Vasily , Ozog David , Tucker Don
Published: July 2015

Advances in human brain neuroimaging for high‐temporal and high‐spatial resolutions will depend on localization of electroencephalography (EEG) signals to their cortex sources. The source localization inverse problem is inherently ill‐posed and depends critically on the modeling of human head electromagnetics. We present a systematic methodology to analyze the main factors and parameters that affect the EEG source‐mapping accuracy. These factors are not independent, and their effect must be evaluated in a unified way. To do so requires significant computational capabilities to explore the problem landscape, quantify uncertainty effects, and evaluate alternative algorithms. Bringing high‐performance computing to this domain is necessary to open new avenues for neuroinformatics research. The head electromagnetics forward problem is the heart of the source localization inverse. We present two parallel algorithms to address tissue inhomogeneity and impedance anisotropy. Highly accurate head modeling environments will enable new research and clinical neuroimaging applications. Cortex‐localized dense‐array EEG analysis is the next‐step in neuroimaging domains such as early childhood reading, understanding of resting‐state brain networks, and models of full brain function. Therapeutic treatments based on neurostimulation will also depend significantly on high‐performance computing integration. Copyright © 2015 John Wiley & Sons, Ltd.
Evaluating ARM HPC clusters for scientific workloads
Authors: Maqbool Jahanzeb , Oh Sangyoon , Fox Geoffrey C.
Published: July 2015

The power consumption of modern high‐performance computing (HPC) systems that are built using power hungry commodity servers is one of the major hurdles for achieving Exascale computation. Several efforts have been made by the HPC community to encourage the use of low‐powered system‐on‐chip (SoC) embedded processors in large‐scale HPC systems. These initiatives have successfully demonstrated the use of ARM SoCs in HPC systems, but there is still a need to analyze the viability of these systems for HPC platforms before a case can be made for Exascale computation. The major shortcomings of current ARM‐HPC evaluations include a lack of detailed insights about performance levels on distributed multicore systems and performance levels for benchmarking in large‐scale applications running on HPC. In this paper, we present a comprehensive evaluation of results that covers major aspects of server and HPC benchmarking for ARM‐based SoCs. For the experiments, we built an unconventional cluster of ARM Cortex‐A9s that is referred to as Weiser and ran single‐node benchmarks (STREAM, Sysbench, and PARSEC) and multi‐node scientific benchmarks (High‐performance Linpack (HPL), NASA Advanced Supercomputing (NAS) Parallel Benchmark, and Gadget‐2) in order to provide a baseline for performance limitations of the system. Based on the experimental results, we claim that the performance of ARM SoCs depends heavily on the memory bandwidth, network latency, application class, workload type, and support for compiler optimizations. During server‐based benchmarking, we observed that when performing memory intensive benchmarks for database transactions, x86 performed 12% better for multithreaded query processing. However, ARM performed four times better for performance to power ratios for a single core and 2.6 times better on four cores. We noticed that emulated double precision floating point in Java resulted in three to four times slower performance as compared with the performance in C for CPU‐bound benchmarks. Even though Intel x86 performed slightly better in computation‐oriented applications, ARM showed better scalability in I/O bound applications for shared memory benchmarks. We incorporated the support for ARM in the MPJ‐Express runtime and performed comparative analysis of two widely used message passing libraries. We obtained similar results for network bandwidth, large‐scale application scaling, floating‐point performance, and energy‐efficiency for clusters in message passing evaluations (NBP and Gadget 2 with MPJ‐Express and MPICH). Our findings can be used to evaluate the energy efficiency of ARM‐based clusters for server workloads and scientific workloads and to provide a guideline for building energy‐efficient HPC clusters. Copyright © 2015 John Wiley & Sons, Ltd.
The Impact of Resonance Stabilization on the Intramolecular Hydrogen‐Atom Shift Reactions of Hydrocarbon Radicals
Authors: Wang Kun , Villano Stephanie M. , Dean Anthony M.
Published: July 2015

A series of intramolecular H‐atom shift reactions of both alkenyl and allylic radicals were investigated by using CBS‐QB3 electronic structure calculations. In the first set of reactions, an alkyl radical site was converted into an allylic radical site. In the second set, an allylic radical was converted into another allylic radical. The results are discussed in the context of a Benson‐type model to examine the impact of the transition‐state partial resonance stabilization on both the activation energies and the pre‐exponential factors. In most cases, the differences in the activation energies relative to those for the analogous alkyl radicals are primarily due to the barriers of the bimolecular reaction component of the activation energy. For the first set of reactions, there is additional entropy loss relative to the alkyl radical analogues. This additional loss of entropy may be smaller than some previous estimates. The pre‐exponential factors for the second set of reactions are generally similar to those of the analogous alkyl radical reactions (once the double bond in the transition state is accounted for).
Effect of Nitrogen Substitution in V2O3 on the Metal–Insulator Transition
Authors: Kumar Nitesh , Sreedhara M. B. , Kouser Summayya , Waghmare Umesh V. , Rao C. N. R.
Published: July 2015

The effect of N‐doping on the paramagnetic–antiferromagnetic transition associated with the metal–insulator (M–I) transition of V2O3 at 150 K has been studied in bulk samples as well as in nanosheets. The magnetic transition temperature of V2O3 is lowered to ∼120 K in the N‐doped samples. Electrical resistivity data also indicate a similar lowering of the M–I transition temperature. First‐principles DFT calculations reveal that anionic (N) substitution and the accompanying oxygen vacancies reduce the energy of the high‐temperature metallic corundum phase relative to the monoclinic one leading to the observed reduction in Nèel temperature. In the electronic structure of N‐substituted V2O3, a sub‐band of 2p states of trivalent anion (N) associated with its strong bond with the vanadium cation appears at the top of the band of O(2p) states, the 3d‐states of V being slightly higher in energy. Its band gap is thus due to crystal field splitting of the degenerate d‐orbitals of vanadium and superexchange interaction, which reduces notably (ΔEg=−0.4 eV) due to their hybridization with the 2p states of nitrogen. A weak magnetic moment arises in the monoclinic phase of N‐substituted V2O3 with O‐vacancies, with a moment of −1 μB/N localized on vanadium atoms in the vicinity of oxygen vacancies.
CdSe Quantum Dots and N719‐Dye Decorated Hierarchical TiO2 Nanorods for the Construction of Efficient Co‐Sensitized Solar Cells
Authors: Subramaniam Mohan Raj , Kumaresan Duraisamy
Published: July 2015

Three‐dimensional hierarchical TiO2 nanorods (HTNs) decorated with the N719 dye and 3‐mercaptopropionic or oleic acid capped CdSe quantum dots (QDs) in photoanodes for the construction of TiO2 nanorod‐based efficient co‐sensitized solar cells are reported. These HTN co‐sensitized solar cells showed a maximum power‐conversion efficiency of 3.93 %, and a higher open‐circuit voltage and fill factor for the photoanode with 3‐mercaptopropionic acid capped CdSe QDs due to the strong electronic interactions between CdSe QDs, N719 dye and HTNs, and the superior light‐harvesting features of the HTNs. An electrochemical impedance analysis indicated that the superior charge‐collection efficiency and electron diffusion length of the CdSe QD‐coated HTNs improved the photovoltaic performance of these HTN co‐sensitized solar cells.
CdSeTe@CdS@ZnS Quantum‐Dot‐Sensitized Macroporous Tio2 Film: A Multisignal‐Amplified Photoelectrochemical Platform
Authors: Zhou Shiwei , Wang Yingying , Zhao Ming , Jiang Li‐Ping , Zhu Jun‐Jie
Published: July 2015

A macroporous TiO2 film (M‐TiO2), which was prepared by burning off the polystyrene microsphere (PS) template from a PS/TiO2 composite film, can provide a large active surface, improve electron‐transport performance, and increase the photocurrent. Furthermore, core–shell–shell CdSeTe@CdS@ZnS quantum dots (QDs) were introduced to sensitize the M‐TiO2 film, which can efficiently broaden the absorption spectra range, separate and transfer charge carriers, reduce recombination loss, and improve photovoltaic response, with a sensitization shell of CdS and a passivation shell of ZnS. A multisignal‐amplified photoelectrochemical platform was fabricated by further modifying this film with a combination of biotin–DEVD–peptide (Biotin–Gly–Asp–Gly–Asp–Glu–Val–Asp–Gly–Cys) (which is specifically cleaved by caspase‐3) and streptavidin‐labeled alkaline phosphatase (SA‐ALP). Under the enzymatic catalysis of ALP with the substrate 2‐phospho‐L‐ascorbic acid trisodium salt (AAP), ascorbic acid (AA) was generated as a better electron donor, leading to increased photocurrent output. The activity of caspase‐3, which depends on the amount of residual peptide on the electrode, was inversely proportional to the amount of AA. By monitoring the variation of photocurrent caused by AA, caspase‐3 activity and the therapeutic effect of nilotinib (a special medicine of chronic myeloid leukemia, CML) were indirectly detected and evaluated. The photoelectrochemical platform can be used as a potential evaluation system for monitoring caspase‐3 activity and drug effects.
Material Clocking by Silica Nanoparticle Precipitation in Solution Phase that is Tunable by Organic Molecules
Authors: Miyagawa Masamichi , Yamaguchi Masahiko
Published: July 2015

Material clocking is an important biological phenomenon through which the structure of a material changes sharply with time after activation. A suspension of silica (P)‐nanoparticles in the presence of organic molecules in solution exhibits such a material clocking phenomenon during delayed precipitation with high accuracy and precision. A mixture of ethynylhelicene (P)‐pentamer and silica (P)‐nanoparticles with an average diameter of 70 nm grafted with (P)‐helicene in trifluoromethylbenzene is sonicated for activation and dispersion. The (P)‐nanoparticles start to precipitate after 3 h of settling at 25 °C and precipitate completely after 4 h. UV/Vis, CD, and DLS analyses of the process show no change during the initial 3 h, but then an abrupt stair‐shaped kinetic change occurs with concomitant precipitation and removal of the (P)‐pentamer from the solution phase. The delay in the precipitation can be tuned by the structure of molecules added to the (P)‐nanoparticle suspension.
Crystal structure, spectroscopic studies and non‐linear optical properties of 2‐amino‐3‐nitropyridinium trichloroacetate
Authors: Song Cheng , Zhou Yuelan , Sun Zhihua , Chen Tianliang , Zhang Shuquan , Luo Junhua
Published: July 2015

A new quadratic nonlinear optical crystal, 2‐amino‐3‐nitropyridinium trichloroacetate (2A3NPTCA), was synthesized and the single crystals were grown by slow evaporation method at room temperature. Single crystal X‐ray diffraction and powder X‐ray diffraction experiments were carried out in order to confirm the structure and crystalline nature of 2A3NPTCA crystal. The chemical bonding and various functional groups present in the 2A3NPTCA were identified from FT‐IR spectrum. The UV–visible–NIR transmission spectrum shows that it is suitable for frequency‐converting in the wavelength region of 431–1200 nm. Thermogravimetric (TG) and differential thermal analysis (DTA) were carried out to characterize the thermal behaviors of the grown crystals. Kurtz and Perry powder method for second harmonic generation (SHG) measurements demonstrate that 2A3NPTCA is a phase matching material and its nonlinear optical efficiency is two times that of KDP. All the above results suggest that 2A3NPTCA is a potential candidate of NLO material.
Li‐Metal‐Free Prelithiation of Si‐Based Negative Electrodes for Full Li‐Ion Batteries
Authors: Zhou Haitao , Wang Xuehang , Chen De
Published: July 2015

Most of the high‐capacity positive‐electrode materials [for example, S, O2 (air), and MOx (M: V, Mn, Fe, etc.)] are Li‐deficient and require the use of a Li‐metal electrode or prelithiation. Herein, we report a novel electrolytic cell in which the Si electrode can be prelithiated in a well‐controlled manner from Li‐containing aqueous solution in a Li‐metal‐free way. MnOx/Si and S/Si Li‐ion full cells were assembled by using the prelithiated Si negative electrodes, which resulted in high specific energies of 349 and 732 Wh kg−1, respectively. The MnOx/Si full cell still retains 138 Wh kg−1 even at a high specific power of 1710 W kg−1. This is the first report of a whole process of making a full Li‐ion battery with both Li‐deficient electrodes without the use of Li metal as the Li source. This novel prelithiation process, with high controllability, no short circuiting, and an abundant Li source, is expected to contribute significantly to the development of safe, green, and powerful Li‐ion batteries.
Gas Transfer Controls Carbon Limitation During Biomass Production by Marine Microalgae
Authors: Tamburic Bojan , Evenhuis Christian R. , Suggett David J. , Larkum Anthony W. D. , Raven John A. , Ralph Peter J.
Published: July 2015

This study presents the first in‐depth analysis of CO2 limitation on the biomass productivity of the biofuel candidate marine microalga Nannochloropsis oculata. Net photosynthesis decreased by 60 % from 125 to 50 μmol L−1 h−1 over a 12 h light cycle as a direct result of carbon limitation. Continuous dissolved O2 and pH measurements were used to develop a detailed diurnal mechanism for the interaction between photosynthesis, gas exchange and carbonate chemistry in the photo‐bioreactor. Gas exchange determined the degree of carbon limitation experienced by the algae. Carbon limitation was confirmed by delivering more CO2, which increased net photosynthesis back to its steady‐state maximum. This study highlights the importance of maintaining replete carbon concentrations in photo‐bioreactors and other culturing facilities, either by constant pH operation or preferably by designing a feedback loop based on the dissolved O2 concentration.
Fade to Green: A Biodegradable Stack of Microbial Fuel Cells
Authors: Winfield Jonathan , Chambers Lily D. , Rossiter Jonathan , Stinchcombe Andrew , Walter X. Alexis , Greenman John , Ieropoulos Ioannis
Published: July 2015

The focus of this study is the development of biodegradable microbial fuel cells (MFCs) able to produce useful power. Reactors with an 8 mL chamber volume were designed using all biodegradable products: polylactic acid for the frames, natural rubber as the cation‐exchange membrane and egg‐based, open‐to‐air cathodes coated with a lanolin gas diffusion layer. Forty MFCs were operated in various configurations. When fed with urine, the biodegradable stack was able to power appliances and was still operational after six months. One useful application for this truly sustainable MFC technology includes onboard power supplies for biodegradable robotic systems. After operation in remote ecological locations, these could degrade harmlessly into the surroundings to leave no trace when the mission is complete.
Selective Deposition of Insulating Metal Oxide in Perovskite Solar Cells with Enhanced Device Performance
Authors: Yue Youfeng , Yang Xudong , Wu Yongzhen , Salim Noviana Tjitra , Islam Ashraful , Noda Takeshi , Han Liyuan
Published: July 2015

We report a simple methodology for the selective deposition of an insulating layer on the nanoparticulate TiO2 (np‐TiO2) mesoporous layer of perovskite solar cells. The deposited MgO insulating layer mainly covered the bottom part of the np‐TiO2 layer with less coverage at the top. The so‐called quasi‐top‐open structure is introduced to act as an efficient hole‐blocking layer to prevent charge recombination at the physical contact of the transparent conducting oxide with the perovskite. This leads to an open‐circuit voltage higher than that of the reference cell with a compact TiO2 hole‐blocking layer. Moreover, such a quasi‐top‐open structure can facilitate the electron injection from perovskite into the np‐TiO2 mesoporous layer and improve the spectral response at longer wavelength because of the less covered insulating layer at the top. This work provides an alternative way to fabricate perovskite solar cells without the need to use a conventional compact TiO2 layer.
Enhanced Performance of “Flower‐like” Li4Ti5O12 Motifs as Anode Materials for High‐Rate Lithium‐Ion Batteries
Authors: Wang Lei , Zhang Yiman , Scofield Megan E. , Yue Shiyu , McBean Coray , Marschilok Amy C. , Takeuchi Kenneth J. , Takeuchi Esther S. , Wong Stanislaus S.
Published: July 2015

“Flower‐like” motifs of Li4Ti5O12 were synthesized by using a facile and large‐scale hydrothermal process involving unique Ti foil precursors followed by a short, relatively low‐temperature calcination in air. Moreover, a detailed time‐dependent growth mechanism and a reasonable reaction scheme were proposed to clearly illustrate and highlight the structural evolution and subsequent formation of this material. Specifically, the resulting “flower‐like” Li4Ti5O12 microspheres consisting of thin nanosheets provide for an enhanced surface area and a reduced lithium‐ion diffusion distance. The high surface areas of the exposed roughened, thin petal‐like component nanosheets are beneficial for the interaction of the electrolyte with Li4Ti5O12, which thereby ultimately provides for improved high‐rate performance and favorable charge/discharge dynamics. Electrochemical studies of the as‐prepared nanostructured Li4Ti5O12 clearly revealed their promising potential as an enhanced anode material for lithium‐ion batteries, as they present both excellent rate capabilities (delivering 148, 141, 137, 123, and 60 mAh g−1 under discharge rates of 0.2, 10, 20, 50, and 100 C, at cycles of 50, 55, 60, 65, and 70, respectively) and stable cycling performance (exhibiting a capacity retention of ≈97 % from cycles 10–100, under a discharge rate of 0.2 C, and an impressive capacity retention of ≈87 % by using a more rigorous discharge rate of 20 C from cycles 101–300).
Multitarget fluorescence in situ hybridization assay for the detection of lung cancer in bronchial cytology specimens
Authors: Zhai Jing
Published: July 2015

Background

Routine bronchial cytology is an important diagnostic tool in suspected lung cancer. The purpose of this study is to evaluate the performance of LAVysion FISH assay over routine cytology for the detection of malignant bronchial cytology specimens.

Methods

Forty six patients who underwent bronchoscopic examination in a period of 6 months were included. Bronchial brushing and/or washing specimens were accompanied by concurrent endobronchial biopsy and/or FNA, which were used as gold standard for diagnosis. The smears for FISH assay were made from the discarded residual fluid after being processed for routine cytology.

Results

Twenty seven of the 46 patients were diagnosed of malignancy. For bronchial brushing specimens, the sensitivity of routine cytology and FISH for the detection of malignancy was 18% (3/17) and 35% (6/17) respectively (p = 0.08); the specificity of routine cytology and FISH was the same, 80% (8/10). For bronchial washing specimens, the sensitivity of routine cytology and FISH for the detection of malignancy was 8% (2/24) and 29% (7/24) respectively (p = 0.01); the specificity of routine cytology and FISH was the same, 94% (16/17).

Conclusions

Our data shows that routine bronchial cytology appears to have a very low sensitivity for the detection of malignancy. FISH assay appears to increase the sensitivity for the detection of malignancy, but does not appear to improve it to a desirable level. A larger prospective study is necessary to further evaluate the role of FISH assay in the detection of malignancy in bronchial cytology specimens. Diagn. Cytopathol. 2015;43:819–824. © 2015 Wiley Periodicals, Inc.
Easily Vaporizable Ionic Liquids – No Contradiction!
Authors: Köckerling Martin , Peppel Tim , Thiele Philipp , Verevkin Sergey P. , Emel'yanenko Vladimir N. , Samarov Artemiy A. , Ruth Wolfgang
Published: July 2015

It was a big surprise to see crystals of an ionic liquid (IL) forming by sublimation at room temperature. ILs are generally accepted to have negligible vapour pressures at elevated temperatures, making their sublimation or distillation very difficult. ILs that sublime easily contain silylimidazolium‐based cations. In order to establish the details of the unusual behaviour of this subclass of ILs, a combined spectroscopic, X‐ray crystallographic, physicochemical and theoretical characterization was performed. The results are compared with those of other easily vaporizable compounds, like ammonium chloride and naphthalene. The single‐crystal X‐ray structure analysis of one of these compounds, N‐methyl‐N′‐dimethyl(phenyl)silylimidazolium chloride (monoclinic, C2/c), clearly shows the existence of isolated ions, demonstrating that the compound is an ionic liquid.
Synthesis and Characterization of GaIII, InIII and LuIII Complexes of a Set of dtpa Bis‐Amide Ligands
Authors: Greiser Julia , Hagemann Tino , Niksch Tobias , Traber Philipp , Kupfer Stephan , Gräfe Stefanie , Görls Helmar , Weigand Wolfgang , Freesmeyer Martin
Published: July 2015

The synthesis and characterization of five new diethylenetriaminepentaacetic acid (dtpa) ligands, (dtpa)‐N,N″‐bis(alkoxyphenylamide), and their complexation with GaIII, InIII and LuIII are reported. The procedures for the synthesis of all complexes in aqueous media are described as well as a synthetic pathway for the preparation of GaIII complexes in chloroform. All substances were characterized by NMR spectroscopy, mass spectrometry, elemental analysis and HPLC. Single‐crystal structure analysis was performed where applicable, which revealed the presence of hepta‐ and octa‐coordinated isomers for InIII complexes and a nine‐fold coordination of LuIII ions in the solid state. Additional NMR experiments suggested a hepta‐coordinated InIII species in solution, whereas the GaIII complexes appear to be hexa‐coordinated and the LuIII complexes to be octa‐coordinated. Both NMR and HPLC studies indicated the presence of a single isomer in every complex.