bluuebunny/crossref_metadata_2025_split huggingface dataset:
Easy Access to the Copper(III) Anion [Cu(CF3)4]−
Authors: Romine Andrew M. , Nebra Noel , Konovalov Andrey I. , Martin Eddy , Benet‐Buchholz Jordi , Grushin Vladimir V. 
Published: January 2015

AbstractCuCl or pre‐generated CuCF3 reacts with CF3SiMe3/KF in DMF in air to give [Cu(CF3)4]− quantitatively. [PPN]+, [Me4N]+, [Bu4N]+, [PhCH2NEt3]+, and [Ph4P]+ salts of [Cu(CF3)4]− were prepared and isolated spectroscopically and analytically pure in 82–99 % yield. X‐ray structures of the [PPN]+, [Me4N]+, [Bu4N]+, and [Ph4P]+ salts were determined. A new synthetic strategy with [Cu(CF3)4]− was demonstrated, involving the removal of one CF3− from the Cu atom in the presence of an incoming ligand. A novel CuIII complex [(bpy)Cu(CF3)3] was thus prepared and fully characterized, including by single‐crystal X‐ray diffraction. The bpy complex is highly fluxional in solution, the barrier to degenerate isomerization being only 2.3 kcal mol−1. An NPA study reveals a huge difference in the charge on the Cu atom in [Cu(CR3)4]− for R=F (+0.19) and R=H (+0.46), suggesting a higher electron density on Cu in the fluorinated complex.
Fluoride‐Promoted Esterification with Imidazolide‐Activated Compounds: A Modular and Sustainable Approach to Dendrimers
Authors: García‐Gallego Sandra , Hult Daniel , Olsson Johan V. , Malkoch Michael 
Published: January 2015

AbstractBased on the growing demand for facile and sustainable synthetic methods to structurally perfect polymers, we herein describe a significant improvement of esterification reactions capitalizing on 1,1′‐carbonyldiimidazole (CDI). Cesium fluoride was shown to be an essential catalyst for these reactions to reach completion. This approach was successfully applied to the synthesis of structurally flawless and highly functional polyester dendrimers employing traditional and accelerated growth strategies. A sixth generation bis‐MPA dendrimer with a molecular weight of 22.080 Da and 192 peripheral hydroxy groups was isolated in less than one day of total reaction time. Large quantities of dendrimerswere obtained in high yields (>90 %) using simple purification steps under sustainable conditions. The fluoride‐promoted esterification (FPE) via imidazolide‐activated compounds is wide in scope and constitutes a potentially new approach toward functional polymers and other materials.
Carbo‐Quinoids: Stability and Reversible Redox‐Proaromatic Character towards Carbo‐Benzenes
Authors: Cocq Kévin , Maraval Valérie , Saffon‐Merceron Nathalie , Saquet Alix , Poidevin Corentin , Lepetit Christine , Chauvin Remi 
Published: January 2015

AbstractThe carbo‐mer of the para‐quinodimethane core is stable within in a bis(9‐fluorenylidene) derivative. Oxidation of this carbo‐quinoid with MnO2 in the presence of SnCl2 and ethanol affords the corresponding p‐bis(9‐ethoxy‐fluoren‐9‐yl)‐carbo‐benzene. The latter can be in turn converted back into the carbo‐quinoid by reduction with SnCl2, thus evidencing a chemical reversibility of the interconversion between a pro‐aromatic carbo‐quinoid and an aromatic carbo‐benzene, and is reminiscent of the behavior of the benzoquinone/hydroquinone redox couple (in the red–ox opposite sense).
Functionalization of Liquid‐Exfoliated Two‐Dimensional 2H‐MoS2
Authors: Backes Claudia , Berner Nina C. , Chen Xin , Lafargue Paul , LaPlace Pierre , Freeley Mark , Duesberg Georg S. , Coleman Jonathan N. , McDonald Aidan R. 
Published: January 2015

AbstractLayered two‐dimensional (2D) inorganic transition‐metal dichalchogenides (TMDs) have attracted great interest as a result of their potential application in optoelectronics, catalysis, and medicine. However, methods to functionalize and process such 2D TMDs remain scarce. We have established a facile route towards functionalized layered MoS2. We found that the reaction of liquid‐exfoliated 2D MoS2, with M(OAc)2 salts (M=Ni, Cu, Zn; OAc=acetate) yielded functionalized MoS2–M(OAc)2 materials. Importantly, this method furnished the 2H‐polytype of MoS2 which is a semiconductor. X‐ray photoelectron spectroscopy (XPS), diffuse reflectance infrared Fourier transform spectroscopy (DRIFT–IR), and thermogravimetric analysis (TGA) provide strong evidence for the coordination of MoS2 surface sulfur atoms to the M(OAc)2 salt. Interestingly, functionalization of 2H‐MoS2 allows for its dispersion/processing in more conventional laboratory solvents.
Lithium Imide Synergy with 3d Transition‐Metal Nitrides Leading to Unprecedented Catalytic Activities for Ammonia Decomposition
Authors: Guo Jianping , Wang Peikun , Wu Guotao , Wu Anan , Hu Daqiang , Xiong Zhitao , Wang Junhu , Yu Pei , Chang Fei , Chen Zheng , Chen Ping 
Published: January 2015

AbstractAlkali metals have been widely employed as catalyst promoters; however, the promoting mechanism remains essentially unclear. Li, when in the imide form, is shown to synergize with 3d transition metals or their nitrides TM(N) spreading from Ti to Cu, leading to universal and unprecedentedly high catalytic activities in NH3 decomposition, among which Li2NHMnN has an activity superior to that of the highly active Ru/carbon nanotube catalyst. The catalysis is fulfilled via the two‐step cycle comprising: 1) the reaction of Li2NH and 3d TM(N) to form ternary nitride of LiTMN and H2, and 2) the ammoniation of LiTMN to Li2NH, TM(N) and N2 resulting in the neat reaction of 2 NH3⇌N2+3 H2. Li2NH, as an NH3 transmitting agent, favors the formation of higher N‐content intermediate (LiTMN), where Li executes inductive effect to stabilize the TMN bonding and thus alters the reaction energetics.
Remarkably Enhanced Gas Separation by Partial Self‐Conversion of a Laminated Membrane to Metal–Organic Frameworks
Authors: Liu Yi , Pan Jia Hong , Wang Nanyi , Steinbach Frank , Liu Xinlei , Caro Jürgen 
Published: January 2015

AbstractSeparation methods based on 2D interlayer galleries are currently gaining widespread attention. The potential of such galleries as high‐performance gas‐separation membranes is however still rarely explored. Besides, it is well recognized that gas permeance and separation factor are often inversely correlated in membrane‐based gas separation. Therefore, breaking this trade‐off becomes highly desirable. Here, the gas‐separation performance of a 2D laminated membrane was improved by its partial self‐conversion to metal–organic frameworks. A ZIF‐8‐ZnAl‐NO3 layered double hydroxide (LDH) composite membrane was thus successfully prepared in one step by partial conversion of the ZnAl‐NO3 LDH membrane, ultimately leading to a remarkably enhanced H2/CH4 separation factor and H2 permeance.
Zinc(II)‐Catalyzed Intermolecular Hydrative Aldol Reactions of 2‐En‐1‐ynamides with Aldehydes and Water to form Branched Aldol Products Regio‐ and Stereoselectively
Authors: Jadhav Appaso Mahadev , Pagar Vinayak Vishnu , Huple Deepak B. , Liu Rai‐Shung 
Published: January 2015

AbstractThis work describes zinc(II)‐catalyzed hydrative aldol reactions of 2‐en‐1‐ynamides with aldehydes and water to afford branched aldol products regio‐ and stereoselectively. The anti and syn selectivity can be modulated by the sizes of sulfonamides to yield E‐ and Z‐configured zinc(II) dienolates selectively. This new reaction leads to enantiopure aldol products by using a cheap chiral sulfonamide. The mechanistic analysis reveals that the sulfonamide amides of the substrates can trap a released proton to generate dual acidic sites to activate a carbonyl allylation reaction.
Reversible Morphological Transformation between Polymer Nanocapsules and Thin Films through Dynamic Covalent Self‐Assembly
Authors: Kim Jeehong , Baek Kangkyun , Shetty Dinesh , Selvapalam Narayanan , Yun Gyeongwon , Kim Nam Hoon , Ko Young Ho , Park Kyeng Min , Hwang Ilha , Kim Kimoon 
Published: January 2015

AbstractA facile method has been developed for synthesizing polymer nanocapsules and thin films using multiple in‐plane stitching of monomers by the formation of reversible disulfide linkages. Owing to the reversibility of the disulfide linkages, the nanostructured materials readily transform their structures in response to environmental changes at room temperature. For example, in reducing environments, the polymer nanocapsules release loaded cargo molecules. Moreover, reversible morphological transformations between these structures can be achieved by simple solvent exchanges. This work is a novel approach for the formation of robust nano/microstructured materials that dynamically respond to environmental stimuli.
Characterization and strain‐energy‐function‐based modeling of the thermomechanical response of shape‐memory polymers
Authors: Pulla Sesha S. , Souri Mohammad , Karaca Haluk E. , Lu Y. Charles 
Published: January 2015

ABSTRACTShape‐memory polymers (SMPs) are an emerging class of active polymers that can be used on a wide range of reconfigurable structures and actuation devices. In this study, an epoxy‐based SMP was synthesized, and its thermomechanical behaviors were comprehensively characterized. The stress–strain behavior of the SMP was determined to be nonlinear, finite deformation in all regions. Strain‐energy‐based models were used to capture the complicated stress–strain behavior and shape‐recovery response of the SMP. Among various strain energy functions, the stretch‐based Ogden model provided the best fit to the experimental observations. Compared to the sophisticated models developed for SMPs, the strain‐energy‐based model was found to be reliable and much easier to use for practical SMP designs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41861.
Different dispersion polymerization strategies influence the quality of fluorescent poly (St‐co‐GMA) microspheres
Authors: Peng Gang , Wang Bin , Meng Xu , Liu Bailing , Luo Rong 
Published: January 2015

ABSTRACTThe polymerization strategy plays a vital role in the preparation of functional microspheres. In this work, fluorescent poly (styrene‐co‐glycidyl methacrylate) (PSt‐GMA) microspheres were synthesized via one‐stage and two‐stage dispersion polymerization with 4‐Bis(5‐phenyl‐1,3‐oxazol‐2‐yl)benzene (POPOP) as fluorescence agent. SEM and DLS were adopted to characterize the properties of prepared microspheres. The UV‐vis and fluorescence spectroscopy were used to analyze the mechanisms of two‐stage dispersion polymerization. The experimental results showed that the size distribution and fluorescence intensity of prepared microspheres could be improved by two‐stage dispersion polymerization compared to one‐stage dispersion polymerization. In addition, according to UV‐vis, the interactions between POPOP and Poly (N‐vinyl pyrrolidone) (PVP) as well as POPOP and Glycidyl methacrylate (GMA) could affect the particle size and its distribution. UV‐vis and fluorescence spectra implied that the POPOP existed outside of the particle's core via two‐stage strategy. The monomer conversion of styrene was similar at the beginning of reaction; however, the monomer conversion of styrene by two‐stage strategy was higher than that of by one‐stage strategy. In a word, two‐stage dispersion polymerization could prepare fluorescent microspheres with the monodispersion micrometer‐size and high quality. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41927.
Synthesis of hydrophilic to superhydrophobic SU8 surfaces
Authors: Kumar Vijay , Sharma Niti Nipun 
Published: January 2015

ABSTRACTIn published literature, it is widely reported that the plasma treatment and funtionalization with Octadecyltrichlorosilane (OTS) self‐assembled monolayer (SAM) can individually alter the wetting properties of SU8 surface. A combination of the two approaches gives better results and the synergism of the two approaches produces a superhydrophobic SU8 surface, which is presented in this work. We have investigated various composition of plasma for treatment of SU8 surfaces and permuted the treated SU8 surfaces with deposition of OTS SAM. In all such synergized experiments, we obtained water contact angle higher than 150°, which is much higher than the one that can be obtained with individual application of the two approaches. The combined approach presented in this work is suitable for bulk production of superhydrophobic surface, and is a mask‐less process, which makes it cost effective. The surface topography, wetting, and chemical properties of SU8 surfaces were characterized using the contact angle goniometry, atomic force microscopy, FTIR, Raman, and XPS spectra. The superhydrophobic SU8 surfaces were observed to be stable even after five months. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41934.
Input Shaping of the Synchronous Generator for Reduction of Self‐induced Oscillations
Authors: Jolevski Danijel , Bego Ozren 
Published: January 2015

AbstractThis article suggests the application of input shaping for the elimination of electromechanical oscillations arising from changes in the operating point of the synchronous generator. Poorly damped poles are the cause of electromechanical oscillations of the synchronous generator. Various power system stabilizers (PSS) are now used to reduce the electromechanical oscillations. Input shaping is a feedforward control and therefore does not require the measurement of electrical and mechanical quantities of the synchronous generator unlike the PSS. It is possible to apply the input shaping for the excitation system of synchronous generators with or without PSS.
Ten-year follow-up results of a randomized clinical trial comparing left thoracoabdominal and abdominal transhiatal approaches to total gastrectomy for adenocarcinoma of the oesophagogastric junction or gastric cardia
Authors:   Japan Clinical Oncology Group (JCOG9502), Kurokawa Y , Sasako M , Sano T , Yoshikawa T , Iwasaki Y , Nashimoto A , Ito S , Kurita A , Mizusawa J , Nakamura K 
Published: January 2015

Abstract

Background
The optimal surgical approach for treatment of oesophagogastric junction (OGJ) cancer is controversial. A randomized clinical trial (JCOG9502) comparing transhiatal (TH) and left thoracoabdominal (LTA) approaches was stopped after the first interim analysis owing to limited efficacy for LTA resections. Complete 10-year follow-up data are now available.

Methods
Patients with histologically proven adenocarcinoma of the OGJ or gastric cardia with oesophageal invasion of 3 cm or less were randomized to a TH or LTA approach. Both groups underwent total gastrectomy and splenectomy with D2 nodal dissection plus para-aortic lymphadenectomy above the left renal vein. For LTA, a thorough mediastinal lymphadenectomy below the left inferior pulmonary vein was also mandatory. The primary endpoint was overall survival.

Results
A total of 167 patients (82 TH, 85 LTA) were enrolled. The 10-year overall survival rate was 37 (95 per cent c.i. 26 to 47) per cent for the TH approach and 24 (15 to 34) per cent for the LTA technique (P = 0·060). The hazard ratio for death was 1·42 (0·98 to 2·05) for the LTA technique. Subgroup analysis based on the Siewert classification indicated non-significant survival advantages in favour of the TH approach.

Conclusion
LTA resections should be avoided in the treatment of adenocarcinoma of the OGJ or gastric cardia. Registration number: NCT00149266 (https://www.clinicaltrials.gov).
Probing the Molecular Mechanisms in Copper Amine Oxidases by Generating Heterodimers
Authors: Gaule Thembaninkosi G. , Smith Mark A. , Pearson Arwen R. , Knowles Peter F. , McPherson Michael J. 
Published: January 2015

AbstractFor some homodimeric copper amine oxidases (CuAO), there is suggestive evidence of differential activity at the two active sites implying potential cooperativity between the two monomers. To examine this phenomenon for the Arthrobacter globiformis CuAO (AGAO), we purified a heterodimeric form of the enzyme for comparison with the homodimer. The heterodimer comprises an active wild‐type monomer and an inactive monomer in which an active‐site tyrosine is mutated to phenylalanine (Y382F). This mutation prevents the formation of the trihydroxyphenylalanine quinone (TPQ) cofactor. A pETDuet vector and a dual fusion tag strategy was used to purify heterodimers (WT/Y382F) from homodimers. Purity was confirmed by western blot and native PAGE analyses. Spectral and kinetic studies support the view that whether there are one or two functional monomers in the dimer, the properties of each functional monomer are the same, thus indicating no communication between the active sites in this bacterial enzyme.
Comparative analysis of effects of cyclic uniaxial and equiaxial stretches on gene expression of human umbilical vein endothelial cells
Authors: Shojaei Shahrokh , Tafazzoli‐Shahdpour Mohammad , Shokrgozar Mohammad Ali , Haghighipour Nooshin 
Published: January 2015

AbstractIt has been well established that biomechanical environment can influence functionality of biological cells. There are evidences that show mechanical cyclic stretch can promote smooth muscle cell (SMC) markers in endothelial cells (ECs). The objective of this study was to determine whether mechanical stimuli in the forms of uniaxial and equiaxial cyclic stretches (UNCS and EQCS) can affect endothelial and smooth muscle gene expressions in mRNA level of human umbilical vein endothelial cells (HUVECs). For this purpose, 10% uniaxial UNCS and EQCS (60 cycles/min for 24 h) were applied on HUVECs, and using real‐time PCR expressions of three EC specific markers, vascular endothelial growth factor receptor‐2 (VEGFR‐2, also known as FLK‐1), von Willebrand Factor (vWF) and vascular endothelial‐cadherin (VE‐cadherin) and two SMC specific genes, α‐smooth muscle actin (α‐SMA) and smooth muscle myosin heavy chain (SMMHC) were quantified. Moreover, alterations in cell height were analyzed by atomic force microscopy (AFM). Results showed that cyclic UNCS for 24 h downregulated the expression of all EC markers and upregulated the expression of all SMC markers while low effects on HUVECs height were observed. Cyclic EQCS in the same conditions resulted in minor effect on SMC gene expression in HUVECs, while led to strong reduction in vWF with no significant change in other two endothelial genes. Cyclic EQCS considerably elevated cell height. Results proposed that ECs can transdifferentiate to SMC phenotype under specific microenvironmental conditions.
Boron Nitride Nanoplatelets as a Solid Radical Initiator for the Aerobic Oxidation of Thiophenol to Diphenyldisulfide
Authors: Dhakshinamoorthy Amarajothi , Primo Ana , Esteve‐Adell Ivan , Alvaro Mercedes , Garcia Hermenegildo 
Published: January 2015

AbstractBoron nitride (BN) nanoplatelets suspended in ethanol were obtained through the sonication of BN powders prepared through biopolymer‐templated pyrolysis and air calcination of (NH4)3BO3–chitosan powders. AFM measurements indicate that BN nanoplatelets have an average height of 1.5 nm and length and width dimensions between 30 and 100 nm. BN nanoplatelets exhibit higher catalytic activity for the molecular oxygen‐mediated oxidation of aromatic thiols to the corresponding disulfides than do boron and nitrogen‐codoped graphene or commercial bulk hexagonal BN. The reaction scope includes substituted aromatic and heteroaromatic thiols, whereas aliphatic thiols are considerably less reactive. The hot filtration test and radical quenching by N‐tert‐butyl‐α‐phenylnitrone support an autoxidation mechanism involving thiyl radicals. BN nanoplatelets are deactivated during the course of the reaction owing to aggregation. The present study uncovers the activity of BN nanoplatelets used as an insoluble radical initiator of SH bonds.
Copper Ion Cementation in Presence of a Magnetic Field
Authors: Fadali Olfat A. , Obaid Mohamed , Mahmoud Mohamed S. , Farrag Taha E. , TaeWoo Kim , Khalil Khalil Abdelrazek , Barakat Nasser A. M. 
Published: January 2015

AbstractThe effect of an electromagnetic field (EMF) on the rate of copper(II) cementation from copper sulfate solutions on a rotating iron cylinder was investigated. The studied variables were cylinder rotation speed, magnetic field strength, and magnetic field direction. The application of EMF increased the rate of cementation in both parallel and perpendicular direction of the magnetic field where the latter proved to be more effective. The rate of mass transfer under an EMF was found to be more than doubled. The enhancement of copper recovery in presence of the EMF is due to the induced motion of Fe+n in the solution which is limited to a certain range of cylinder rotation speed. The power consumption for cementation of copper could be significantly reduced by utilizing EMF.
A Polyoxometalate‐Encapsulating Cationic Metal–Organic Framework as a Heterogeneous Catalyst for Desulfurization
Authors: Hao Xiu‐Li , Ma Yuan‐Yuan , Zang Hong‐Ying , Wang Yong‐Hui , Li Yang‐Guang , Wang En‐Bo 
Published: January 2015

AbstractA new cationic triazole‐based metal–organic framework encapsulating Keggin‐type polyoxometalates, with the molecular formula [Co(BBPTZ)3][HPMo12O40]⋅24 H2O [compound 1; BBPTZ=4,4′‐bis(1,2,4‐triazol‐1‐ylmethyl)biphenyl] is hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X‐ray diffraction, and single‐crystal X‐ray diffraction. The structure of compound 1 contains a non‐interpenetrated 3D CdSO4 (cds)‐type framework with two types of channels that are interconnected with each other; straight channels that are occupied by the Keggin‐type POM anions, and wavelike channels that contain lattice water molecules. The catalytic activity of compound 1 in the oxidative desulfurization reaction indicates that it is not only an effective and size‐selective heterogeneous catalyst, but it also exhibits distinct structural stability in the catalytic reaction system.
Selective Oxidation of Alkyl‐Substituted Polyaromatics Using Ruthenium‐Ion‐Catalyzed Oxidation
Authors: Nowicka Ewa , Sankar Meenakshisundaram , Jenkins Robert L. , Knight David W. , Willock David J. , Hutchings Graham J. , Francisco Manuel , Taylor Stuart H. 
Published: January 2015

AbstractInvited for the cover of this issue is the group of Stuart H. Taylor at the Cardiff Catalysis Institute of Cardiff University. The image depicts the selective ruthenium‐ion‐catalyzed oxidation of a range of alkylated polyaromatic hydrocarbons. RuO4 targets oxidation of aromatic carbon in preference to aliphatic carbon. Read the full text of the article at 10.1002/chem.201405831.
Classification of Additives for Organic Photovoltaic Devices
Authors: Machui Florian , Maisch Philipp , Burgués‐Ceballos Ignasi , Langner Stefan , Krantz Johannes , Ameri Tayebeh , Brabec Christoph J. 
Published: January 2015

AbstractThe use of additives to improve the performance of organic photovoltaic cells has been intensely researched in recent years. However, so far, no system has been reported for the classification of additives and their functions. In this report, a system for classifying additives according to the fundamental mechanism by which they influence microstructure formation for P3HT:PCBM is suggested. The major parameters used for their classification are solubility and drying kinetics. Both are discussed in detail and their consequences on processing are analyzed. Furthermore, a general mechanism to classify the impact of additives on structure formation is suggested and discussed for different materials relevant to organic photovoltaic devices.
Enhancing Catalytic Activity by Narrowing Local Energy Gaps—X‐Ray Studies of a Manganese Water Oxidation Catalyst
Authors: Xiao Jie , Khan Munirah , Singh Archana , Suljoti Edlira , Spiccia Leone , Aziz Emad F. 
Published: January 2015

AbstractChanges in the local electronic structure of the Mn 3d orbitals of a Mn catalyst derived from a dinuclear MnIII complex during the water oxidation cycle were investigated ex situ by X‐ray absorption spectroscopy (XAS) and resonant inelastic X‐ray scattering (RIXS) analyses. Detailed information about the Mn 3d orbitals, especially the local HOMO–LUMO gap on Mn sites revealed by RIXS analyses, indicated that the enhancement in catalytic activity (water oxidation) originated from the narrowing of the local HOMO–LUMO gap when electrical voltage and visible light illumination were applied simultaneously to the Mn catalytic system.