bluuebunny/crossref_metadata_2025 huggingface dataset:
Optically Active Tetra‐tert‐butyl‐P5‐deltacyclene Epimers: Preparation, Spectroscopy, Dynamic Equilibriums, H/D Exchange, and Transition‐Metal Complex Chemistry
Authors: Rohwer Lars , Höhn Christine , Autschbach Jochen , Bauer Walter , Heinemann Frank W. , Huguet Torrell Sergi , Keller Irene , Shubina Tatyana E. , Steffen Jacob , Zenneck Ulrich
Published: March 2014

On the basis of isolated diastereomeric triorganylstannyl‐P5‐deltacyclenes 7′ and 7′′, almost pure enantiomers of their destannylation products 8′ and 8′′ are now available. These stereochemically inert cage chiral species contain a configurationally labile P1H1 group that defines two epimers 8 a and 8 b of each of the enantiomers, which are connected by a rapid equilibrium. Mirror‐symmetric circular dichroism (CD) spectra of the enantiomeric cages are compatible with the identification of epimers. A simulation of the CD spectrum of the major epimer 8′a relates the cage chirality of the system to the observed chiroptical effects. Both cage epimers and two of the phosphorus cage atoms are active as ligands with respect to [M(CO)5] fragments of Cr, Mo, and W. Four almost isoenergetic regio‐ and stereoisomers of the resulting mononuclear complexes are formed for these metals, but only one of the isomers per metal crystallized in the case of the racemic series of the complexes. The enantiopure versions of cages and cage complexes, however, did not crystallize at all, a well‐known phenomenon for chiral compounds. CD spectra of the optically active complex isomer mixtures are close to identical with the CD spectra of the related free cages and point again to the chiral cages as the dominant source of the CD effects of the complexes. [(Benzene)RuCl2] complexes of the cage ligand 8 behave totally differently. Only a single species 12=[(benzene)RuCl2⋅8 b] is formed in almost quantitative yield and the minor epimer 8 b plays the role of the ligand exclusively. The reaction works as well for the separated enantiomeric cage versions to yield the highly enriched enantiomers 12′ and 12′′ separately. An efficient kinetic resolution process was identified as the main reason for this finding. It is based on a high stereo‐ and regiochemical flexibility of the PC cage ligand that is capable of adjusting to the specific requirements of a suitable transition‐metal complex fragment. Such ligand flexibility is regularly observed in metalloenzymes, but is a very rare case in classical and organometallic complex chemistry.
Charge‐Transfer Complex Formation in Gelation: The Role of Solvent Molecules with Different Electron‐Donating Capacities
Authors: Basak Shibaji , Bhattacharya Sumantra , Datta Ayan , Banerjee Arindam
Published: March 2014

A naphthalenediimide (NDI)‐based synthetic peptide molecule forms gels in a particular solvent mixture (chloroform/aromatic hydrocarbon, 4:1) through charge‐transfer (CT) complex formation; this is evident from the corresponding absorbance and fluorescence spectra at room temperature. Various aromatic hydrocarbon based solvents, including benzene, toluene, xylene (ortho, meta and para) and mesitylene, have been used for the formation of the CT complex. The role of different solvent molecules with varying electron‐donation capacities in the formation of CT complexes has been established through spectroscopic and computational studies.
Efficient Atropodiastereoselective Access to 5,5′‐Bis‐1,2,3‐triazoles: Studies on 1‐Glucosylated 5‐Halogeno 1,2,3‐Triazoles and Their 5‐Substituted Derivatives as Glycogen Phosphorylase Inhibitors
Authors: Goyard David , Chajistamatiou Aikaterini S. , Sotiropoulou Anastasia I. , Chrysina Evangelia D. , Praly Jean‐Pierre , Vidal Sébastien
Published: March 2014

Whereas copper‐catalyzed azide–alkyne cycloaddition (CuAAC) between acetylated β‐D‐glucosyl azide and alkyl or phenyl acetylenes led to the corresponding 4‐substituted 1‐glucosyl‐1,2,3‐triazoles in good yields, use of similar conditions but with 2 equiv CuI or CuBr led to the 5‐halogeno analogues (>71 %). In contrast, with 2 equiv CuCl and either propargyl acetate or phenyl acetylene, the major products (>56 %) displayed two 5,5′‐linked triazole rings resulting from homocoupling of the 1‐glucosyl‐4‐substituted 1,2,3‐triazoles. The 4‐phenyl substituted compounds (acetylated, O‐unprotected) and the acetylated 4‐acetoxymethyl derivative existed in solution as a single form (d.r.>95:5), as shown by NMR spectroscopic analysis. The two 4‐phenyl substituted structures were unambiguously identified for the first time by X‐ray diffraction analysis, as atropisomers with aR stereochemistry. This represents one of the first efficient and highly atropodiastereoselective approaches to glucose‐based bis‐triazoles as single atropisomers. The products were purified by standard silica gel chromatography. Through Sonogashira or Suzuki cross‐couplings, the 1‐glucosyl‐5‐halogeno‐1,2,3‐triazoles were efficiently converted into a library of 1,2,3‐triazoles of the 1‐glucosyl‐5‐substituted (alkynyl, aryl) type. Attempts to achieve Heck coupling to methyl acrylate failed, but a stable palladium‐associated triazole was isolated and analyzed by 1H NMR and MS. O‐Unprotected derivatives were tested as inhibitors of glycogen phosphorylase. The modest inhibition activities measured showed that 4,5‐disubstituted 1‐glucosyl‐1,2,3‐triazoles bind weakly to the enzyme. This suggests that such ligands do not fit the catalytic site or any other binding site of the enzyme.
High‐Concentration Graphene Dispersions with Minimal Stabilizer: A Scaffold for Enzyme Immobilization for Glucose Oxidation
Authors: Sun Zhenyu , Vivekananthan Jeevanthi , Guschin Dmitrii A. , Huang Xing , Kuznetsov Volodymyr , Ebbinghaus Petra , Sarfraz Adnan , Muhler Martin , Schuhmann Wolfgang
Published: March 2014

Modified acrylate polymers are able to effectively exfoliate and stabilize pristine graphene nanosheets in aqueous media. Starting with pre‐exfoliated graphite greatly promotes the exfoliation level. The graphene concentration is significantly increased up to 11 mg mL−1 by vacuum evaporation of the solvent from the dispersions under ambient temperature. TEM shows that 75 % of the flakes have fewer than five layers with about 18 % of the flakes consisting of monolayers. Importantly, a successive centrifugation and redispersion strategy is developed to enable the formation of dispersions with exceptionally high graphene‐to‐stabilizer ratio. Characterization by high‐resolution transmission electron microscopy, X‐ray photoelectron spectroscopy, X‐ray diffraction, and Raman spectroscopy shows the flakes to be of high quality with very low levels of defects. These dispersions can act as a scaffold for the immobilization of enzymes applied, for example, in glucose oxidation. The electrochemical current density was significantly enhanced to be approximately six times higher than an electrode in the absence of graphene, thus showing potential applications in enzymatic biofuel cells.
Spin‐State Ordering on One Sub‐lattice of a Mononuclear Iron(III) Spin Crossover Complex Exhibiting LIESST and TIESST
Authors: Murnaghan Kevin D. , Carbonera Chiara , Toupet Loic , Griffin Michael , Dîrtu Marinela M. , Desplanches Cédric , Garcia Yann , Collet Eric , Létard Jean‐François , Morgan Grace G.
Published: March 2014

The two‐step spin crossover in mononuclear iron(III) complex [Fe(salpm)2]ClO4⋅0.5 EtOH (1) is shown to be accompanied by a structural phase transition as concluded from 57Fe Mössbauer spectroscopy and single crystal X‐ray diffraction, with spin‐state ordering on just one of two sub‐lattices in the intermediate magnetic and structural phase. The complex also exhibits thermal‐ and light‐induced spin‐state trapping (TIESST and LIESST), and relaxation from the LIESST and TIESST excited states occurs via the broken symmetry intermediate phase. Two relaxation events are evident in both experiments, that is, two T(LIESST) and two T(TIESST) values are recorded. The change in symmetry which accompanies the TIESST effect was followed in real time using single crystal diffraction. After flash freezing at 15 K the crystal was warmed to 40 K at which temperature superstructure reflections were observed to appear and disappear within a 10 000 s time range. In the frame of the international year of crystallography, these results illustrate how X‐ray diffraction makes it possible to understand complex ordering phenomena.
ChemInform Abstract: Above‐Room‐Temperature Ferroelastic Phase Transition in a Perovskite‐Like Compound [N(CH3)4][Cd(N3)3].
Authors: Du Zi‐Yi , Zhao Ying‐Ping , Zhang Wei‐Xiong , Zhou Hao‐Long , He Chun‐Ting , Xue Wei , Wang Bao‐Ying , Chen Xiao‐Ming
Published: March 2014

Block‐shaped single crystals of the new title compound are synthesized by slow evaporation of the filtrate of an aqueous mixture of Cd(NO3)2, NaN3, and Me4NBr in the ratio of 1:12:6 (20 °C, 55% yield).
ChemInform Abstract: [ZnBi4]3‐ Pentagon in K6ZnBi5: Aromatic All‐Metal Heterocycle.
Authors: Qin Qian , Zhou Liujiang , Wang Yi , Sang Ruili , Xu Li
Published: March 2014

The new Zintl phase of title is synthesized from stoichiometric mixtures of the elements (Nb containers, 700 °C, 48 h) and characterized by powder XRD, magnetic measurements, and projector augmented wave band structure computations.
ChemInform Abstract: Carbon—Carbon Bond Formation via Benzoyl Umpolung Attained by Photoinduced Electron‐Transfer with Benzimidazolines.
Authors: Igarashi Tomohito , Tayama Eiji , Iwamoto Hajime , Hasegawa Eietsu
Published: March 2014

It is proposed that electron transfer from a benzimidazoline additive to photoexcited benzoyl compounds (I) generates carbanions which react with alkyl halides to give alkylated alcohols.
ChemInform Abstract: Organocatalytic Michael Addition/Intramolecular Julia—Kocienski Olefination for the Preparation of Nitrocyclohexenes.
Authors: Rodrigo Eduardo , Garcia Ruano Jose Luis , Cid M. Belen
Published: March 2014

Application of this method is demonstrated by the formal total synthesis of Trandolapril (VIII).
ChemInform Abstract: Synthesis and Structure of Large Difluoromethylene Containing Alicycles by Ring Closing Metathesis (RCM).
Authors: Skibinski Maciej , Urbina‐Blanco Cesar A. , Slawin Alexandra M. Z. , Nolan Steven P. , O'Hagan David
Published: March 2014

The ring closing metathesis is applied to long terminal olefins (I) containing bis(thianes) to afford exclusively the corresponding (E)‐olefins (II).
ChemInform Abstract: Anodic Fluorination of 4‐Methoxy‐1‐naphthol and 4‐Nitroanisole Using Et3N·5HF in Mixed Nonaqueous Solvent.
Authors: Saraswat A. , Sharma L. K. , Singh S. , Siddiqui I. R. , Singh R. K. P.
Published: March 2014

The title reaction proceeds in the presence of Et3N·5HF which serves as supporting electrolyte and as fluorine source.
ChemInform Abstract: Asymmetric Michael Addition of Ketones to Nitroolefins Catalyzed by a Novel Chiral Pyrrolidine‐Thiourea in the Ionic Liquid.
Authors: Lu Jun , Chen Wei‐Yi
Published: March 2014

A new catalyst is developed for the asymmetric Michael addition of cyclohexanone and acetone to nitroolefins giving the corresponding nitroolefins with high enantioselectivities.
ChemInform Abstract: Synthesis of N‐Heterocyclic Carbene Silver and Palladium Complexes Bearing Bis(pyrazol‐1‐yl)methyl Moieties.
Authors: Li Qiang , Xie Yun‐Fu , Sun Bao‐Chuan , Yang Jun , Song Hai‐Bin , Tang Liang‐Fu
Published: March 2014

A series of N‐heterocyclic carbene catalysts are screened for the three‐component coupling reaction of aldehydes with piperidine and phenylacetylene to produce propargylamines.
ChemInform Abstract: ortho‐Selective Nucleophilic Addition of Amines to 3‐Borylbenzynes: Synthesis of Multisubstituted Anilines by the Triple Role of the Boryl Group.
Authors: Takagi Akira , Ikawa Takashi , Saito Kozumo , Masuda Shigeaki , Ito Toyohiro , Akai Shuji
Published: March 2014

The investigations reveal that the nucleophilic addition to benzynes, generated in situ from triflate (I), exhibits higher ortho‐selectivities than those of 3‐(trimethylsilyl)benzynes.
ChemInform Abstract: ipso‐Hydroxylation of Arylboronic Acids and Boronate Esters by Using Sodium Chlorite as an Oxidant in Water.
Authors: Gogoi Pranjal , Bezboruah Pranjal , Gogoi Junali , Boruah Romesh C.
Published: March 2014

This is a simple, catalyst‐free, and inexpensive procedure for the title reaction giving the products in high yields without a chromatographic purification.
ChemInform Abstract: An in situ Generated CuI/Metformin Complex as a Novel and Efficient Catalyst for C—N and C—O Cross‐Coupling Reactions.
Authors: Ghorbani‐Vaghei Ramin , Hemmati Saba , Veisi Hojat
Published: March 2014

Metformin is a novel, polydentate nitrogen donor ligand that can be used for N/O‐arylation reactions along with air‐stable and inexpensive copper(I) iodide.
ChemInform Abstract: Ethyl 2,2‐Bis(4‐methylphenylsulfonamido)acetate to Aromatic α‐Amino Acids: Stable Substrates for Catalytic Arylation Reactions.
Authors: Marques Carolina S. , Burke Anthony J.
Published: March 2014

Title compound (I) is converted to a series of α‐amino acids (III) using two catalytic systems.
ChemInform Abstract: Iodine‐Catalyzed Selective Synthesis of 2‐Sulfanylphenols via Oxidative Aromatization of Cyclohexanones and Disulfides.
Authors: Ge Wenlei , Zhu Xun , Wei Yunyang
Published: March 2014

Both aryl and alkyl disulfides are employed as sulfanylation reagents to give the desired products in good yields under the optimized reaction conditions.
ChemInform Abstract: Chiral Bidiaziridines by a Two‐Step Domino Aziridination of meso‐α‐Diimines.
Authors: Aresu Emanuele , Carroccia Laura , Fioravanti Stefania , Gasbarri Simona , Pellacani Lucio , Sciubb Fabio
Published: March 2014

The stereochemical outcome of the aziridination reaction of meso‐α‐diimines is investigated.
ChemInform Abstract: Di‐ and Triheteroarylalkanes via Self‐Condensation and Intramolecular Friedel—Crafts Type Reaction of Heteroaryl Alcohols.
Authors: Dhiman Seema , Ramasastry S. S. V.
Published: March 2014

A general method for the conversion of heteroaryl alcohols (I), (III), and (V) to di‐ and triheteroarylalkanes (II), (IV), (VI), and 1,3‐heteroarylpropenes (VIII) in the presence of highly reactive Yb(OTf)3 catalyst is reported.
ChemInform Abstract: Asymmetric Synthesis of β‐Substituted α‐Methylenebutyrolactones via TRIP‐Catalyzed Allylation: Mechanistic Studies and Application to the Synthesis of (S)‐(‐)‐Hydroxymatairesinol.
Authors: Fuchs Michael , Schober Markus , Orthaber Andreas , Faber Kurt
Published: March 2014

TRIP‐Catalyzed allylation of aldehydes proceeds via in situ generated zinc(II)‐allylbutyrolactone species which is crucial for chiral induction.
ChemInform Abstract: Palladium‐Catalyzed Synthesis of 3‐Acylated Indoles Involving Oxidative Cross‐Coupling of Indoles with α‐Amino Carbonyl Compounds.
Authors: Tang Ri‐Yuan , Guo Xiao‐Kang , Xiang Jian‐Nan , Li Jin‐Heng
Published: March 2014

It provides a new and efficient approach to a series of 3‐acylated indoles.
ChemInform Abstract: Organocatalyzed Synthesis of Isoxazolidin‐5‐ones: The Meldrum′s Acid Approach.
Authors: Postikova Svetlana , Tite Tony , Levacher Vincent , Briere Jean‐Francois
Published: March 2014

Meldrum′s acid is a useful ketene equivalent in the reaction with nitrones to give isoxazolidin‐5‐ones, via a domino anionic formal [3 + 2] cycloaddition‐decarboxylation process.
ChemInform Abstract: Meglumine Promoted One‐Pot, Four‐Component Synthesis of Pyranopyrazole Derivatives.
Authors: Guo Rui‐Yun , An Zhi‐Min , Mo Li‐Ping , Yang Shu‐Tao , Liu Hong‐Xia , Wang Shu‐Xia , Zhang Zhan‐Hui
Published: March 2014

The synthesis of title compounds [(IV), (VI), (VIII), (X), and (XII)] is conveniently and green approached using meglumine as an efficient and inexpensive reusable catalyst.
ChemInform Abstract: One‐Pot Synthesis of Phenylseleno N‐Acetyl α‐Amino Acids: Supra‐Molecular Self‐Assembling in Organoselenium Compounds.
Authors: Prabhu C. Parashiva , Phadnis Prasad P. , Wadawale Amey , Priyadarsini K. Indira , Jain Vimal K.
Published: March 2014

A convenient one‐pot two‐step procedure is developed for the synthesis of the title acids (IV).
ChemInform Abstract: Enantioselective Synthesis of 2‐Substituted‐tetrahydroisoquinolin‐1‐yl Glycine Derivatives via Oxidative Cross‐Dehydrogenative Coupling of Tertiary Amines and Chiral Nickel(II) Glycinate.
Authors: Zhou Shengbin , Wang Jiang , Lin Daizong , Zhao Fei , Liu Hong
Published: March 2014

It provides a new, easy, and highly stereoselective approach to a number of tetrahydroisoquinolinyl glycine derivatives.
ChemInform Abstract: Regio‐ and Stereochemical Controlled Koenigs—Knorr‐Type Monoglycosylation of Secondary Hydroxy Groups in Carbohydrates Utilizing the High Site Recognition Ability of Organotin Catalysts.
Authors: Muramatsu Wataru , Yoshimatsu Hirofumi
Published: March 2014

A Sn‐catalyzed one‐pot process for the monoglycosylation of secondary OH‐groups in carbohydrate is described.
ChemInform Abstract: Saccharonol B, a New Cytotoxic Methylated Isocoumarin from Saccharomonospora azurea.
Authors: Vishwakarma Ram A. , et al. et al.
Published: March 2014

The biological activity of this compound is investigated.
ChemInform Abstract: Anion Receptor Chemistry: Highlights from 2011 and 2012
Authors: Gale Philip A. , Busschaert Nathalie , Haynes Cally J. E. , Karagiannidis Louise E. , Kirby Isabelle L.
Published: March 2014

Review: 114 refs.
ChemInform Abstract: Aluminum Acetals in Organic Synthesis
Authors: Boussonniere Anne , Beneteau Romain , Lebreton Jacques , Denes Fabrice
Published: March 2014

Review: 118 refs.
ChemInform Abstract: Recent Progress in the Synthetic Assembly of 2‐Cyclopentenones
Authors: Aitken David J. , Eijsberg Hendrik , Frongia Angelo , Ollivier Jean , Piras Pier Paolo
Published: March 2014

Review: 164 refs.
ChemInform Abstract: Modification of Biologically Active Plant Metabolites via the Metal Complex Catalysis Reactions as a Promising Direction in Medicinal Chemistry
Authors: Shul'ts E. E. , Tolstikov G. A.
Published: March 2014

Review: 59 refs.
ChemInform Abstract: A Biocompatible, Highly Efficient Click Reaction and Its Applications
Authors: Yuan Yue , Liang Gaolin
Published: March 2014

Review: 21 refs.
ChemInform Abstract: Recent Advances in Molecular Recognition in Water: Artificial Receptors and Supramolecular Catalysis
Authors: Kataev Evgeny A. , Mueller Christoph
Published: March 2014

Review: 164 refs.
ChemInform Abstract: Au/M (M: Ag, Pd, Pt) Bimetallic Nanoparticles with Enhanced Catalytic Activity for Aerobic Glucose Oxidation
Authors: Zhang Haijun , Toshima Naoki
Published: March 2014

Review: 59 refs.
ChemInform Abstract: Merging the Best of Both Worlds: Hybrid Lipid‐Enveloped Matrix Nanocomposites in Drug Delivery
Authors: Raemdonck Koen , Braeckmans Kevin , Demeester Jo , De Smedt Stefaan C.
Published: March 2014

Review: 247 refs.
ChemInform Abstract: Functional Interlocked Systems
Authors: van Dongen Stijn F. M. , Cantekin Seda , Elemans Johannes A. A. W. , Rowan Alan E. , Nolte Roeland J. M.
Published: March 2014

Review: functional aspects and applications of interlocked molecules; 55 refs.
ChemInform Abstract: Matching Chelators to Radiometals for Radiopharmaceuticals
Authors: Price Eric W. , Orvig Chris
Published: March 2014

Review: 321 refs.
ChemInform Abstract: Single Molecule Methods for the Study of Catalysis: From Enzymes to Heterogeneous Catalysts
Authors: Janssen Kris P. F. , De Cremer Gert , Neely Robert K. , Kubarev Alexey V. , Van Loon Jordi , Martens Johan A. , De Vos Dirk E. , Roeffaers Maarten B. J. , Hofkens Johan
Published: March 2014

Review: 55 refs.
Substitutional Doping of Carbon Nanotubes with Heteroatoms and Their Chemical Applications
Authors: Zhang Yexin , Zhang Jian , Su Dang Sheng
Published: March 2014

The electronic properties of carbon nanotubes (CNTs) can be tuned by substitutional doping with heteroatoms (mainly B and N) to expand the applications of CNTs. Based on the comprehensive understanding of the substitutional doping of CNTs, it should be possible to deliberately design doped CNTs for specific purposes. Thus, relevant experimental and theoretical works are reviewed herein in an attempt to correlate the synthetic methods, electronic properties, and applications of heteroatom‐doped CNTs. The distribution and arrangement of heteroatoms in the graphitic lattice of CNTs can be modulated through the choice of synthetic conditions, which would further lead to different electronic properties of CNTs for their chemical applications.
Validation of 31 of the most commonly used immunohistochemical antibodies in cytology prepared using the cellient® automated cell block system
Authors: Montgomery Eric , Gao Chen , de Luca Julie , Bower Jessie , Attwood Kristropher , Ylagan Lourdes
Published: March 2014

The Cellient® cell block system has become available as an alternative, partially automated method to create cell blocks in cytology. We sought to show a validation method for immunohistochemical (IHC) staining on the Cellient cell block system (CCB) in comparison with the formalin fixed paraffin embedded traditional cell block (TCB). Immunohistochemical staining was performed using 31 antibodies on 38 patient samples for a total of 326 slides. Split samples were processed using both methods by following the Cellient® manufacturer's recommendations for the Cellient cell block (CCB) and the Histogel method for preparing the traditional cell block (TCB). Interpretation was performed by three pathologists and two cytotechnologists. Immunohistochemical stains were scored as: 0/1+ (negative) and 2/3+ (positive). Inter‐rater agreement for each antibody was evaluated for CCB and TCB, as well as the intra‐rater agreement between TCB and CCB between observers. Interobserver staining concordance for the TCB was obtained with statistical significance (P < 0.05) in 24 of 31 antibodies. Interobserver staining concordance for the CCB was obtained with statistical significance in 27 of 31 antibodies. Intra‐observer staining concordance between TCB and CCB was obtained with statistical significance in 24 of 31 antibodies tested. In conclusions, immunohistochemical stains on cytologic specimens processed by the Cellient system are reliable and concordant with stains performed on the same split samples processed via a formalin fixed‐paraffin embedded (FFPE) block. The Cellient system is a welcome adjunct to cytology work‐flow by producing cell block material of sufficient quality to allow the use of routine IHC. Diagn. Cytopathol. 2014;42:1024–1033. © 2014 Wiley Periodicals, Inc.
Indium(0)‐Mediated C–S/O Cross‐Coupling Approach Towards the Regioselective Alkylation of α‐Enolic Esters/Dithioesters: A Mechanistic Insight
Authors: Chowdhury Sushobhan , Chanda Tanmoy , Gupta Ashutosh , Koley Suvajit , Ramulu B. Janaki , Jones Raymond C. F. , Singh Maya Shankar
Published: March 2014

We have reported an indium(0)‐mediated C–S/O cross‐coupling approach that leads to the highly regioselective alkylation of α‐enolic acetate/dithioacetate systems. This hetero cross‐coupling reaction does not require additional co‐catalyst or promoter, and the in situ generated organoindium species promotes the reaction by acting as the coupling partner of the α‐enolic acetate/dithioacetate substrates. The excellent selectivity for C‐, S‐, or O‐alkylation is solely dependent on the nucleophilic behavior of α‐enolic acetate/dithioacetate systems. These results were further supported by DFT calculations of the relative electronic energies of the substrates and products as well as the activation barriers of the respective transformations.
Lewis‐Acid‐Catalyzed Benzylic Reactions of 2‐Methylazaarenes with Aldehydes
Authors: Mao Dan , Hong Gang , Wu Shengying , Liu Xin , Yu Jianjun , Wang Limin
Published: March 2014

Lewis‐acid‐catalyzed benzylic reactions of 2‐methylazaarenes with aldehydes have been investigated. Series of azaarene derivatives were afforded by this reaction. 2‐(Pyridin‐2‐yl)ethanols with common substituents were formed through the LiNTf2‐promoted aldol reaction for the first time. 2‐Alkenylpyridines, exclusively in the form of the E isomers, were synthesized in the presence of LiNTf2 cooperated with H2NTf. In the presence of La(Pfb)3 as catalysis, 2‐alkenylquinolines were obtained in high yields through the reactions between 2‐methylquinolines and aldehydes under air.
Titanocene(III) Chloride Mediated Stereoselective Synthesis of Trisubstituted Tetrahydrofurans and a Spirolactone by Tandem Radical Reactions
Authors: Mukherjee Shirshendu , Roy Rajdip , Chandra Roy Subhas
Published: March 2014

The titanocene(III) chloride (Cp2TiCl) mediated stereoselective synthesis of highly substituted tetrahydrofurans has been achieved by a reaction that proceeds through a tandem radical cyclization reaction between a Baylis–Hillman adduct and an activated bromo/iodo compound. The reaction of an epoxide with the Baylis–Hillman adduct furnished a spirolactone through a radical cyclization followed by an in situ lactonization. Cp2TiCl was prepared in situ from commercially available Cp2TiCl2and zinc dust in tetrahydrofuran.
Prediction of site factors by a non‐parametric approach
Authors: Peruš Iztok , Fajfar Peter
Published: March 2014

The problem addressed in this paper is the estimation of the (de)amplification of ground motion at soil sites (compared to rock sites) as a function of the intensity of the ground motion. A non‐parametric empirical approach, called the Conditional Average Estimator (CAE) method, has been used, which is different from all existing approaches. Site factors (SFs) for sites characterized with Vs30 between 180 and 360 m/s were predicted for the peak ground acceleration (PGA) and the spectral accelerations by using a combined database of recorded ground motions. Based on the results of the study, site factors for PGA and selected spectral accelerations are proposed, separately for weaker and stronger ground motions. Comparisons are made with the SFs used in two standards (Eurocode 8 and ASCE 7‐10) and with SFs proposed in the literature, including four Next Generation Attenuation (NGA) ground‐motion prediction equations. The study reveals that (i) SFs depend strongly on the ground‐motion intensity. In the case of stronger ground motions, they decrease with increasing acceleration. (ii) The SFs predicted in this study agree reasonably well with the existing SFs in the case of weak ground motion. For higher intensities of ground motion, they are generally smaller than the existing ones. Copyright © 2014 John Wiley & Sons, Ltd.
Orogen‐scale drainage network evolution and response to erodibility changes: insights from numerical experiments
Authors: Giachetta Emanuele , Refice Alberto , Capolongo Domenico , Gasparini Nicole M. , Pazzaglia Frank J.
Published: March 2014

The continuous feedbacks among tectonics, surface processes, and climate are reflected in the distribution of catchments on active mountain ranges. Previous studies have shown a regularity of valley spacing across mountain ranges worldwide, but the origin of this geomorphological feature is currently not well known. In this work, we use a landscape evolution model to investigate the process of fluvial network organization and the evolution of regular ridge‐and‐valley patterns on simulated mountain ranges. In particular, we investigate the behavior of such patterns when subjected to a perturbation in landscape processes from a previous steady state, resulting from a sudden variation in the pattern of bedrock erodibility, from homogeneous to a gradient. We analyze the time evolution of the mean ratio λ' between the linear spacing of adjacent valleys and the half width of the mountain range. We show how a valley spacing ratio of ~0.5 is first achieved at steady state under uniform bedrock erodibility. After applying the gradient of bedrock erodibility across the landscape, we observe that λ' first increases and then decreases to a new steady‐state value that is smaller than the original value. A detailed analysis of the simulations, through observations of surface ‘snapshots’ at repeated time intervals, allows to gain some insight into the mechanisms governing this fluvial network reorganization process, driven by the migration of the main divide toward the side characterized by lower bedrock erodibility. On both sides of the range the new steady‐state valley spacing is obtained through mechanisms of catchment reorganization and competition between adjacent fluvial networks. In particular, catchment reorganization is characterized by the growth of smaller catchments between shrinking larger catchments on the side with lower erodibility, and the growth of larger catchments on the side with higher erodibility. Copyright © 2014 John Wiley & Sons, Ltd.
Framing the Capacity to Do and Use Evaluation
Authors: Cousins J. Bradley , Goh Swee C. , Elliott Catherine J. , Bourgeois Isabelle
Published: March 2014

The construct of organizational evaluation capacity is a concept that is receiving increasing attention in theoretical and research‐based literature. It is situated within a stream of inquiry that has come to be known as evaluation capacity building (ECB). This chapter reviews evolving conceptions of ECB and recent research and theory in the area. A conceptualization of organizational capacity for evaluation is explicated. The framework addresses not only the capacity to do but also the capacity to use evaluation. This framework has evolved within our ongoing research program and has also informed other research activities focusing on the integration of evaluation into organizational culture. This chapter concludes with a discussion of implications for ongoing research and practice.
Promoting High‐Impact Student Learning: Connecting Key Components of the Collegiate Experience
Authors: Wawrzynski Matthew , Baldwin Roger
Published: March 2014

High‐impact learning practices can connect varied elements of the college environment to create a more coherent educational experience that facilitates student learning.
Effect of inhomogeneity of the electrospun fibrous scaffolds of gelatin/polycaprolactone hybrid on cell proliferation
Authors: Feng Bei , Duan Huichuan , Fu Wei , Cao Yilin , Jie Zhang Wen , Zhang Yanzhong
Published: March 2014

In this article, gelatin (GT) and polycaprolactone (PCL) blended with a weight ratio of 50:50 were dissolved in the trifluoroethanol (TFE) or the acetic acid‐doped TFE solvent system (0.2% relative to TFE) to prepare fibrous scaffolds of GT/PCL with different compositional and morphological homogeneities (denoted as the group 1 and the group 2 scaffolds) by electrospinning. The morphology and composition of the two groups of fibrous scaffolds were examined by scanning electron microscopy and Fourier transform infrared spectroscopy, respectively. Then, using green fluorescence protein‐labeled mouse fibroblasts and HaCaT cells (a human keratinocyte cell line) as the model cells, cell adhesion, morphology, and proliferation were assessed by laser scanning confocal microscopy, scanning electron microscopy, and cell counting kit‐8 assay, respectively. The results showed that the morphological and compositional inhomogeneity of the group 1 scaffolds had a remarkable influence on cell adhesion and proliferation. In contrast, there was no significant difference among the group 2 scaffolds because of their good consistency in fiber morphology and composition. Phase separation resultant GT content variance in the group 1 scaffolds is suggested as one of the major causes. This study highlighted the importance of producing morphologically uniform and compositionally homogeneous composite nanofibers while electrospinning natural and synthetic polymer blends. © 2014 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 103A: 431–438, 2015.
Reduction in Proximal Femoral Strength in Patients With Acute Spinal Cord Injury
Authors: Edwards W Brent , Schnitzer Thomas J , Troy Karen L
Published: March 2014

Bone loss after spinal cord injury (SCI) is associated with an increased risk of fracture resulting from minor trauma. Proximal femoral fractures account for approximately 10% to 20% of the fractures in this population and are among the most serious of injuries. Our purpose was to quantify changes to proximal femoral strength in patients with acute SCI. Thirteen subjects received dual-energy X-ray absorptiometry (DXA) and clinical computed tomography (CT) scans at serial time points during acute SCI separated by a mean of 3.5 months (range 2.6 to 4.8 months). Areal bone mineral density (aBMD) at the proximal femur was quantified from DXA, and proximal femoral strength was predicted using CT-based finite element (FE) modeling in a sideways fall configuration. During the acute period of SCI, femoral neck and total proximal femur aBMD decreased by 2.0 ± 1.1%/month (p < 0.001) and 2.2 ± 0.7%/month (p < 0.001), respectively. The observed reductions in aBMD were associated with a 6.9 ± 2.0%/month (p < 0.001) reduction in femoral strength. Thus, changes in femoral strength were some 3 times greater than the observed changes in aBMD (p < 0.001). It was interesting to note that in just 3.5 months of acute SCI, reductions in strength for some patients were on the order of that predicted for lifetime declines owing to aging. Therefore, it is important that therapeutic interventions are implemented soon after SCI in an effort to halt bone loss and decrease fracture risk. In addition, clinicians utilizing DXA to monitor bone health after SCI should be aware of the potential discrepancy between changes in aBMD and strength. © 2014 American Society for Bone and Mineral Research.
A single‐dose, open‐label, parallel, randomized, dose‐proportionality study of paliperidone after intramuscular injections of paliperidone palmitate in the deltoid or gluteal muscle in patients with schizophrenia
Authors: Cleton Adriaan , Rossenu Stefaan , Crauwels Herta , Berwaerts Joris , Hough David , Gopal Srihari , Eerdekens Marielle , Vandebosch An , Remmerie Bart , De Meulder Marc , Fernández Clara M. Rosso
Published: March 2014

Paliperidone palmitate (PP) is a long‐acting injectable (LAI) antipsychotic, developed for monthly intramuscular (i.m.) administration into deltoid/gluteal muscle, approved for the treatment of schizophrenia in many countries. To assess the options for i.m. injection sites, dose‐proportionality of PP was investigated after injection of a single dose (25–150 mg eq.) of PP in either gluteal (n = 106) or deltoid (n = 95) muscle of schizophrenic patients. Overall, mean (geometric) area under plasma concentration–time curve from time zero to infinity (AUC∞) of paliperidone increased proportionally with increasing PP doses, regardless of injection site. Mean maximum plasma concentration (Cmax) was slightly less than dose‐proportional for both injection sites at PP doses >50 mg eq. Mean Cmax was higher after injection in the deltoid compared with the gluteal muscle, except for the 100 mg eq. dose, while AUC∞ for both injection sites was comparable at all doses. Median time to reach Cmax (tmax) ranged from 13–14 days after deltoid and 13–17 days after gluteal injection across all doses. Single PP injections in deltoid and gluteal muscles in the dose range of 25–150 mg eq. were generally tolerable both locally and systemically.
Highly flexible broadband terahertz metamaterial quarter‐wave plate
Authors: Cong Longqing , Xu Ningning , Gu Jianqiang , Singh Ranjan , Han Jiaguang , Zhang Weili
Published: March 2014

Metamaterials offer exciting opportunities that enable precise control of light propagation, its intensity and phase by designing an artificial medium of choice. Inducing birefringence via engineered metamolecules presents a fascinating mechanism to manipulate the phase of electromagnetic waves and facilitates the design of polarimetric devices. In this paper, a high‐efficiency, broadband, tunable and flexible quarter‐wave plate based on a multilayer metamaterial is presented. Excellent achromatic π/2 phase retardance with high transmission is observed upon terahertz propagation through the quarter‐wave plate. The calculated Stokes parameter represents the output polarization state numerically, indicating an excellent broadband conversion of linearly polarized light into circularly polarized light. The metamaterial‐based quarter‐wave plate demonstrated in this work could be an important step forward in the development of functional terahertz polarization conversion devices for practical applications.
Hybrid femtosecond laser microfabrication to achieve true 3D glass/polymer composite biochips with multiscale features and high performance: the concept of ship‐in‐a‐bottle biochip
Authors: Wu Dong , Wu Si‐Zhu , Xu Jian , Niu Li‐Gang , Midorikawa Katsumi , Sugioka Koji
Published: March 2014

True three‐dimensionally (3D) integrated biochips are crucial for realizing high performance biochemical analysis and cell engineering, which remain ultimate challenges. In this paper, a new method termed hybrid femtosecond laser microfabrication which consists of successive subtractive (femtosecond laser‐assisted wet etching of glass) and additive (two‐photon polymerization of polymer) 3D microprocessing was proposed for realizing 3D “ship‐in‐a‐bottle” microchip. Such novel microchips were fabricated by integrating various 3D polymer micro/nanostructures into flexible 3D glass microfluidic channels. The high quality of microchips was ensured by quantitatively investigating the experimental processes containing “line‐to‐line” scanning mode, improved annealing temperature (645°C), increased prebaking time (18 h for 1mm‐length channel), optimal laser power (1.9 times larger than that on the surface) and longer developing time (6 times larger). The ship‐in‐a‐bottle biochips show high capabilities to provide simultaneous filtering and mixing with 87% efficiency in a shorter distance and on‐chip synthesis of ZnO microflower particles.
Towards A Pan–Cultural Personality Structure: Input from 11 Psycholexical Studies
Authors: De Raad Boele , Barelds Dick P. H. , Timmerman Marieke E. , De Roover Kim , Mlačić Boris , Church A. Timothy
Published: March 2014

The purpose of the present study is to find the common kernel of different trait taxonomic studies and find out how the individual structures relate to this common kernel. Trait terms from 11 psycholexically based taxonomies were all translated into English. On the basis of the commonalities in English, the 11 matrices were merged into a joint matrix with 7104 subjects and 1993 trait terms. Untranslatable terms produced large areas with missing data. To arrive at the kernel structure of the joint matrix, a simultaneous component analysis was applied. In addition, the kernel structures were compared with the individual taxonomy trait structures, obtained via principal component analysis. The findings provide evidence of a structure consisting of three components to stand out as the core of the taxonomies included in this study; those components were named dynamism, affiliation, and order. Moreover, the relations between these three kernel components and those of a six–component solution (completing the six–factor model) are provided. Copyright © 2014 European Association of Personality Psychology
Exposure to traffic and early life respiratory infection: A cohort study
Authors: Rice Mary B. , Rifas‐Shiman Sheryl L. , Oken Emily , Gillman Matthew W. , Ljungman Petter L. , Litonjua Augusto A. , Schwartz Joel , Coull Brent A. , Zanobetti Antonella , Koutrakis Petros , Melly Steven J. , Mittleman Murray A. , Gold Diane R.
Published: March 2014

We examined whether proximity to a major roadway and traffic density around the home during pregnancy are associated with risk of early life respiratory infection in a pre‐birth cohort in the Boston area. We geocoded addresses for 1,263 mother‐child pairs enrolled during the first trimester of pregnancy in Project Viva during 1999–2002. We calculated distance from home to nearest major roadway and traffic density in a 100 m buffer around the home. We defined respiratory infection as maternal report of ≥1 doctor‐diagnosed pneumonia, bronchiolitis, croup, or other respiratory infection from birth until the early childhood visit (median age 3.3). We used relative risk regression models adjusting for potential confounders to estimate associations between traffic exposures and risk of respiratory infection. Distance to roadway during pregnancy was associated with risk of respiratory infection. In fully adjusted models, relative risks (95% CI) for respiratory infection were: 1.30 (1.08, 1.55) for <100 m, 1.15 (0.93, 1.41) for 100 to <200 m, and 0.95 (0.84, 1.07) for 200 to <1,000 m compared with living ≥1,000 m away from a major roadway. Each interquartile range increase in distance to roadway was associated with an 8% (95% CI 0.87, 0.98) lower risk, and each interquartile range increase in traffic density was associated with a 5% (95% CI 0.98, 1.13) higher risk of respiratory infection. Our findings suggest that living close to a major roadway during pregnancy may predispose the developing lung to infection in early life. Pediatr Pulmonol. 2015; 50:252–259. © 2014 Wiley Periodicals, Inc.
Androgen withdrawal fails to induce detectable tissue hypoxia in the rat prostate
Authors: Regter Sietze , Hedayati Mohammad , Zhang Yonggang , Zhou Haoming , Dalrymple Susan , Koch Cameron J. , Isaacs John T. , DeWeese Theodore L.
Published: March 2014

BACKGROUND

It has been reported that significant hypoxia may occur in the rat prostate following androgen deprivation (AD). It is well known that hypoxia substantially reduces radiation sensitivity of cells both in vitro and in vivo. Given that contemporary management of men with intermediate and high‐risk prostate cancer includes the use of neoadjuvant androgen suppression and radiation, AD‐induced hypoxia in the prostate could result in suboptimal therapeutic results. Given this concern, we fully investigate possible AD‐induced hypoxia in the ventral prostate (VP) of adult rats by two independent methods.

METHODS

Tissue pO2 levels in the VP of adult Spraque‐Dawley rats were evaluated prior to and at various time points following castration by two independent techniques. First, an Oxylab tissue oxygen monitor with a 240 μm probe was used for quantitative monitoring of global VP oxygenation. Second, fluorescence immunohistochemistry using the hypoxia marker EF5, known to be metabolically activated by hypoxic cells, was used to evaluate cell‐to‐cell variation in hypoxia at various days post‐castration.

RESULTS

Neither the oxygen probe nor EF5 method demonstrate any substantive change in pO2 levels in the rat VP at any time point post‐castration.

CONCLUSIONS

We find no evidence that the rat VP becomes hypoxic at any point following castration using an animal model that closely mimics the human prostate. These data are in contrast to previous reports suggesting prostatic hypoxia occurs following AD and provide assurance that our present therapeutic strategy of neoadjuvant AD followed by radiation is not compromised by AD‐induced tissue hypoxia. Prostate 74:805–810, 2014. © 2014 Wiley Periodicals, Inc.
Remarkable magnetic properties of amorphous hydrogenated carbon nanostructured thin films
Authors: Lukitsa Ivan , Nikolaychuk Galina , Moroz Oleg
Published: March 2014

Amorphous hydrogenated carbon thin films with 3d metal nanoparticles were deposited on Si and glass‐ceramic substrates by reactive ion‐plasma magnetron sputtering. Thin films have a high complex permittivity ε * and permeability µ * (ε ′ ≈ 1000–10000, ε″ ≈ 100–1500, μ ′ ≈ 10–70, µ ″ ≈ 0.4–10), what can stipulate by anomalous electromagnetic microwave radiation absorption effect. The magnetic parameters as shape of hysteresis loop, values of coercive force, remanence and saturation magnetization were determined from vibrating‐coil magnetometer measurements. The mechanism of absorption in the material under study is described. Obtained results demonstrate a good promise to use this material for the absorption of electromagnetic microwave radiation. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Pathways for novel magnetocaloric materials: A processing prospect
Authors: Krautz Maria , Hosko Josef , Skokov K. , Svec Peter , Stoica Mihai , Schultz Ludwig , Eckert Jürgen , Gutfleisch Oliver , Waske Anja
Published: March 2014

Composites of two magnetocaloric components have been prepared by melt spinning. A special nozzle modification allows to separate the melts of two different materials which solidify simultaneously as rapidly quenched composite. Two materials combinations were chosen: (a) Fe‐based amorphous materials with different Cr‐contents and (b) Fe‐based alloys with different Si‐content resulting in crystalline La(Fe,Si)13 phase with large magnetocaloric effect after subsequent annealing. By melt spinning crystalline segments of several cm length and long amorphous ribbons were obtained. The magnetocaloric properties of the composites were assessed by magnetometry and direct measurements of the adiabatic temperature change. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Towards the large scale production of (La1‐zCez)(Fe1‐x‐yMnySix)13Hn products for room temperature refrigeration
Authors: Mayer Charlotte , Dubrez Alexandra , Pierronnet Michel , Vikner Peter
Published: March 2014

In this paper, we present a novel process based on gas atomization and powder metallurgy techniques to produce reliable and stable (La1‐zCez)(Fe1‐x‐yMnySix)13Hn materials, with 0.08 ≤ x ≤ 0.15, 0 ≤ y ≤ 0.05, 0 ≤ z ≤ 0.3 and 1.5 ≤ n ≤ 3. With this process, shaped pieces ready‐to‐use into refrigeration devices can be produced. Gas atomisation is a rapid solidification technique that prevents the La‐Fe‐Si‐type alloy from forming very large α‐Fe dendrites during cooling, allowing to easily and efficiently heat treat the obtained powder to form the magnetocaloric NaZn13‐type intermetallic. In this process, a batch of 500 kg of alloy was first gas atomized into powder. The powder was then annealed at 1373 K under Ar for one hour to reach around 95% of magnetocaloric phase, and subsequently hydrogenated. Finally, the powder was shaped into composite shaped products containing 91.5 wt.% of powder, by extrusion. This process induces no loss of matter and allows producing non fragile pieces comprising thin portions. Our first results on the stability of partially hydrogenated (La,Ce)(Fe,Mn,Si)13 materials are shown and we discuss on the possible existence of conditions of instability liked to both the composition of the magnetocaloric phase and the level of hydrogenation. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Global assimilation of air temperature, humidity, wind and pressure from surface stations
Authors: Ingleby Bruce
Published: March 2014

Originally the only surface data assimilated in the Met Office global forecasting system were pressure and marine winds but now most temperatures, humidities and land winds are also used. Adjustments for differences between station and model height are essential for pressure and temperature; new height adjustments for humidity and wind were introduced. These changes brought the global and regional forecasting systems much closer in their use of surface data and forecast performance for surface variables. Winds from islands and headlands not resolved in the forecast model and tropical land winds are excluded. Extra reports (notably Metars) have been introduced into the system.

The assimilation of land station temperature and humidity reports gave a clear improvement to short‐range forecasts of ‘screen’ temperature and humidity and small improvements to pressure forecasts. The assimilation of winds over land areas had little impact—wind speed biases, especially at night, are part of the problem. The surface pressure assimilation improves pressure and upper atmosphere forecasts but has little effect on other surface variables. The observation innovations reveal aspects of observation and model errors and other factors such as the proximity to the coast and the importance of the diurnal cycle.