bluuebunny/crossref_metadata_2025_split huggingface dataset:
A case of gingival cancer with pulmonary metastases that developed complete atrioventricular block and ventricular fibrillation as a result of myocardial metastases
Authors: Yoneda Taro , Kase Kazumasa , Amino Yoshiaki , Ogawa Naohiko , Watanabe Satoshi , Hara Johsuke , Abo Miki , Sone Takashi , Kimura Hideharu , Kasahara Kazuo 
Published: October 2016

Key Clinical MessageWe present a rare case of gingival cancer with pulmonary metastases that developed life‐threatening complete atrioventricular block and ventricular fibrillation as a result of myocardial metastases. This case suggests that implantable cardioverter defibrillators significantly improve the quality of life in these patients and maintain their performance status.
Operating the blues
Authors: Chatzis Andrew C. , Kanakis Meletios A. , Sofianidou Joanne , Tsoutsinos Alexandros J. 
Published: October 2016

Key Clinical MessageA 63‐year‐old man bearing most signs and symptoms (facial pigmentation, degenerative arthritis, and dark urine) pertinent to his known history of alkaptonuria underwent aortic valve replacement for critical aortic stenosis. Although rare, aortic stenosis is the most common cardiac manifestation of alkaptonuric ochronosis.
N‐Substituted Azacalixphyrins: Synthesis, Properties, and Self‐Assembly
Authors: Chen Zhongrui , Haddoub Rose , Mahé Jérôme , Marchand Gabriel , Jacquemin Denis , Andeme Edzang Judicaelle , Canard Gabriel , Ferry Daniel , Grauby Olivier , Ranguis Alain , Siri Olivier 
Published: October 2016

AbstractPre‐ and postintroduction of substituents with respect to the macrocyclization step leads to previously unknown N‐substituted azacalixphyrins. The stepwise synthetic approach has been studied in detail to highlight the key role of the N‐substituents of the precursors and/or intermediates in terms of reactivity. Based on a combined experimental and theoretical investigation, the relationship between the properties of the macrocycles and their degree of substitution is rationalized. Depending on the nature of the N‐substituents, the formation of supramolecular ribbon‐like structures could also be observed, as demonstrated by combined TEM, SEM, AFM, and FTIR experiments.
Torsional and Electronic Factors Control the C−H⋅⋅⋅O Interaction
Authors: Driver Russell W. , Claridge Timothy D. W. , Scheiner Steve , Smith Martin D. 
Published: October 2016

AbstractThe precise role of non‐conventional hydrogen bonds such as the C−H⋅⋅⋅O interaction in influencing the conformation of small molecules remains unresolved. Here we survey a series of β‐turn mimetics using X‐ray crystallography and NMR spectroscopy in conjunction with quantum calculation, and conclude that favourable torsional and electronic effects are important for the population of states with conformationally influential C−H⋅⋅⋅O interactions. Our results also highlight the challenge in attempting to deconvolute a myriad of interdependent noncovalent interactions in order to focus on the contribution of a single one. Within a small molecule that is designed to resemble the complexity of the environment within peptides and proteins, the interplay of different steric burdens, hydrogen‐acceptor/‐donor properties and rotational profiles illustrate why unambiguous conclusions based solely on NMR chemical shift data are extremely challenging to rationalize.
Mechanistic Investigation of Molybdate‐Catalysed Transfer Hydrodeoxygenation
Authors: Larsen Daniel B. , Petersen Allan R. , Dethlefsen Johannes R. , Teshome Ayele , Fristrup Peter 
Published: October 2016

AbstractThe molybdate‐catalysed transfer hydrodeoxygenation (HDO) of benzyl alcohol to toluene driven by oxidation of the solvent isopropyl alcohol to acetone has been investigated by using a combination of experimental and computational methods. A Hammett study that compared the relative rates for the transfer HDO of five para‐substituted benzylic alcohols was carried out. Density‐functional theory (DFT) calculations suggest a transition state with significant loss of aromaticity contributes to the lack of linearity observed in the Hammett study. The transfer HDO could also be carried out in neat PhCH2OH at 175 °C. Under these conditions, PhCH2OH underwent disproportionation to yield benzaldehyde, toluene, and significant amounts of bibenzyl. Isotopic‐labelling experiments (using PhCH2OD and PhCD2OH) showed that incorporation of deuterium into the resultant toluene originated from the α position of benzyl alcohol, which is in line with the mechanism suggested by the DFT study.
The Role of Reduced Graphite Oxide in Transition Metal Oxide Nanocomposites Used as Li Anode Material: An Operando Study on CoFe2O4/rGO
Authors: Permien Stefan , Indris Sylvio , Neubüser Gero , Fiedler Andy , Kienle Lorenz , Zander Stefan , Doyle Stephen , Richter Björn , Bensch Wolfgang 
Published: October 2016

AbstractA composite consisting of CoFe2O4 spinel nanoparticles and reduced graphite oxide (rGO) is studied as an anode material during Li uptake and release by applying synchrotron operando X‐ray diffraction (XRD) and operando X‐ray absorption spectroscopy (XAS), yielding a comprehensive picture of the reaction mechanisms. In the early stages of Li uptake, a monoxide is formed as an intermediate phase containing Fe2+ and Co2+ ions; this observation is in contrast to reaction pathways proposed in the literature. In the fully discharged state, metallic Co and Fe nanoparticles are embedded in an amorphous Li2O matrix. During charge, metallic Co and Fe are oxidized simultaneously to Co2+ and Fe3+, respectively, thus enabling a high and stable capacity to be achieved. Here, evidence is presented that the rGO acts as a support for the nanoparticles and prevents the particles from contact loss. The operando investigations are complemented by TEM, Raman spectroscopy, galvanostatic cycling, and cyclic voltammetry.
Biogenic Manganese‐Oxide Mineralization is Enhanced by an Oxidative Priming Mechanism for the Multi‐Copper Oxidase, MnxEFG
Authors: Tao Lizhi , Simonov Alexandr N. , Romano Christine A. , Butterfield Cristina N. , Fekete Monika , Tebo Bradley M. , Bond Alan M. , Spiccia Leone , Martin Lisandra L. , Casey William H. 
Published: October 2016

AbstractIn a natural geochemical cycle, manganese‐oxide minerals (MnOx) are principally formed through a microbial process, where a putative multicopper oxidase MnxG plays an essential role. Recent success in isolating the approximately 230 kDa, enzymatically active MnxEFG protein complex, has advanced our understanding of biogenic MnOx mineralization. Here, the kinetics of MnOx formation catalyzed by MnxEFG are examined using a quartz crystal microbalance (QCM), and the first electrochemical characterization of the MnxEFG complex is reported using Fourier transformed alternating current voltammetry. The voltammetric studies undertaken using near‐neutral solutions (pH 7.8) establish the apparent reversible potentials for the Type 2 Cu sites in MnxEFG immobilized on a carboxy‐terminated monolayer to be in the range 0.36–0.40 V versus a normal hydrogen electrode. Oxidative priming of the MnxEFG protein complex substantially enhances the enzymatic activity, as found by in situ electrochemical QCM analysis. The biogeochemical significance of this enzyme is clear, although the role of an oxidative priming of catalytic activity might be either an evolutionary advantage or an ancient relic of primordial existence.
Reinterpretation of Dynamic Vibrational Spectroscopy to Determine the Molecular Structure and Dynamics of Ferrocene
Authors: Best Stephen P. , Wang Feng , Islam M. Tauhidul , Islam Shawkat , Appadoo Dominique , Trevorah Ryan M. , Chantler Christopher T. 
Published: October 2016

AbstractMolecular distortion of dynamic molecules gives a clear signature in the vibrational spectra, which can be modeled to give estimates of the energy barrier and the sensitivity of the frequencies of the vibrational modes to the reaction coordinate. The reaction coordinate method (RCM) utilizes ab initio‐calculated spectra of the molecule in its ground and transition states together with their relative energies to predict the temperature dependence of the vibrational spectra. DFT‐calculated spectra of the eclipsed (D5h) and staggered (D5d) forms of ferrocene (Fc), and its deuterated analogue, within RCM explain the IR spectra of Fc in gas (350 K), solution (300 K), solid solution (7–300 K), and solid (7–300 K) states. In each case the D5h rotamer is lowest in energy but with the barrier to interconversion between rotamers higher for solution‐phase samples (ca. 6 kJ mol−1) than for the gas‐phase species (1–3 kJ mol−1). The generality of the approach is demonstrated with application to tricarbonyl(η4‐norbornadiene)iron(0), Fe(NBD)(CO)3. The temperature‐dependent coalescence of the ν(CO) bands of Fe(NBD)(CO)3 is well explained by the RCM without recourse to NMR‐like rapid exchange. The RCM establishes a clear link between the calculated ground and transition states of dynamic molecules and the temperature‐dependence of their vibrational spectra.
Amphiphilic Diblock Co‐polymers Bearing a Cysteine Junction Group: Synthesis, Encapsulation of Inorganic Nanoparticles, and Near‐Infrared Photoresponsive Properties
Authors: Geng Yi , Wang Zhi‐Fei , Lin Bao‐Ping , Yang Hong 
Published: October 2016

AbstractEncapsulation of inorganic nanoparticles (NPs) in the interfaces of amphiphilic vesicles is a challenging task. The traditional strategy is to use amphiphilic triblock co‐polymers, which possess two outer blocks for building the walls and coronas of the vesicles, and one middle NP binding block for localizing NPs at the vesicle interfaces. In this manuscript, we describe the design and synthesis of an amphiphilic diblock co‐polymer, that is, PEG‐SH‐b‐PS (PEG=poly(ethylene glycol), PS=polystyrene) bearing a cysteine junction with one free pendant thiol group at the center point between the hydrophilic poly(ethylene glycol) block and the hydrophobic polystyrene block. The amphiphilicity‐driven self‐assembly in aqueous solution of the pure linear diblock co‐polymer PEG‐SH‐b‐PS and the corresponding amphiphilic PEG‐SH‐b‐PS/gold NPs (GNPs) nanocomposites is examined. From TEM observations of the self‐assembled samples containing the conjugated GNPs, it can be concluded that most of the GNPs are dispersed at the interfaces of the formed vesicles. In addition, near‐infrared (NIR)‐absorbing copper monosulfide (CuS) NPs are also encapsulated into the PEG‐SH‐b‐PS vesicles. Due to the photothermal heating effect of the CuS NPs, the corresponding PEG‐SH‐b‐PS/CuSNPs vesicles can disassemble and release the embedded cargos under NIR illumination, which endows this nanocomposite material with potential in biomedical applications, such as cancer imaging, photothermal therapy, and drug delivery.
A DFT Mechanistic Study on Ethylene Tri‐ and Tetramerization with Cr/PNP Catalysts: Single versus Double Insertion Pathways
Authors: Britovsek George J. P. , McGuinness David S. 
Published: October 2016

AbstractThe mechanism of ethylene trimerization and tetramerization with a chromium–diphosphinoamine (Cr–PNP) catalyst system has been studied by theoretical (DFT) methods. Two representative ligands have been explored, namely Ph2PN(Me)PPh2 and (o‐MeC6H4)2PN(Me)P(o‐MeC6H4)2. Calculations on the former ligand reveal how a combination of single and double ethylene insertion mechanisms may lead to 1‐hexene, 1‐octene and the major side products (cyclopentanes and n‐alkanes). For the latter ligand, introduction of o‐alkyl substitution leads to a more sterically congested active species, which suppresses the available pathways for tetramerization and side product formation. Hence, the high selectivity of o‐aryl substituted PNP ligands for trimerization can be rationalized.
Structures, Lewis Acidities, Electrophilicities, and Protecting Group Abilities of Phenylfluorenylium and Tritylium Ions
Authors: Follet Elsa , Mayer Peter , Berionni Guillaume 
Published: October 2016

AbstractThe isolation, characterization, and the first X‐ray structures of a fluorenylium ion and its Lewis adducts with nitrogen‐ and phosphorus‐centered Lewis bases are reported. Kinetics of the reactions of a series of fluorenylium ions with reference π‐, σ‐, and n‐nucleophiles of various sizes and nucleophilicities allowed the interplay between electronic and structural parameters on the electrophilicities of these planarized tertiary carbenium ions to be elucidated. Structure–reactivity correlations and extensive comparisons of their reactivities with those of di‐ and triarylcarbenium ions are described. Quantitative determination of the electrofugalities of fluorenylium ions revealed to which extent they are complementing tritylium ions as protecting groups and how their tuning is possible. Determination of the equilibrium constants of the Lewis adducts formation between pyridines of calibrated Lewis basicities and phenylfluorenylium and tritylium ions allowed the determination of their Lewis acidities and to showcase the potential of these carbon‐centered Lewis acids in catalysis.
Supramolecular Virus‐Like Nanorods by Coassembly of a Triblock Polypeptide and Reversible Coordination Polymers
Authors: Hernandez‐Garcia Armando , Velders Aldrik H. , Stuart Martien A. Cohen , de Vries Renko , van Lent Jan W. M. , Wang Junyou 
Published: October 2016

AbstractWe investigate a new case of a self‐assembly‐stimulated self‐assembly in which a triblock polypeptide is combined with a anionic coordination polymer of a dipicolinic acid bis‐ligand, and d‐ or f‐ block metal ions like ZnII or EuIII. The polypeptide not only has a silk‐like domain that can fold and stack, but also a C‐terminal cationic sequence by which it can interact with the supramolecular (coordination) polyanion. In the presence of all three ingredients (polypeptide, bis‐ligand, and metal ions), we observe the initiation and slow growth of well‐defined metal‐containing nanorods of up to 150 nm in length, proving that self‐assembly of the polypeptide is triggered by the self‐assembly of the coordination polyelectrolyte and vice versa. The particles, which have a striking resemblance to rod‐like viruses, are stable up to 1.2 m NaCl, and can be made fluorescent when lanthanides like EuIII are used, showing the potential to exploit functional properties and applications of virus‐like supramolecular structures.
Monomeric Cinchona Alkaloid‐Based Catalysts for Highly Enantioselective Bromolactonisation of Alkynes
Authors: Wilking Michael , Daniliuc Constantin G. , Hennecke Ulrich 
Published: October 2016

AbstractThe cinchona alkaloid dimer (DHQD)2PHAL has been shown to be a broadly applicable catalyst for asymmetric halogenations. However, this catalyst does not have to be dimeric and a class of monomeric quinidine and quinine‐derived catalysts was prepared, often showing superior selectivity in bromolactonisations of terminal alkynoic acids. Mechanistic investigations show that these organocatalysts act as host molecules that can bind carboxylic acid‐based substrates as guests with substantial binding constants. Based on these findings, it is proposed that this class of catalysts is bifunctional in nature activating the halogenating agent as well as the nucleophile in electrophilic halogenation reactions.
Encapsulation and Enhanced Luminescence Properties of IrIII Complexes within a Hexameric Self‐Assembled Capsule
Authors: Horiuchi Shinnosuke , Tanaka Hirotaka , Sakuda Eri , Arikawa Yasuhiro , Umakoshi Keisuke 
Published: October 2016

AbstractEncapsulation and luminescence studies of [Ir(ppy)2(bpy)]Cl (ppy=2‐phenylpyridinate, bpy=2,2′‐bipyridine) within a hexameric resorcinarene capsule are reported. One IrIII complex cation was encapsulated within the capsule, as demonstrated by NMR and dynamic light scattering (DLS) studies. The emission color of the IrIII complex was drastically changed from orange to yellow by encapsulation, in contrast with the lack of significant changes in the absorption spectrum. The hexameric capsule effectively hampers the non‐radiative pathway to increase both the luminescence quantum yield and the exited state lifetime. The luminescent properties of the encapsulated IrIII complex depend on the ratio of IrIII complex to the resorcinarene monomer as well as the concentration of resorcinarene monomer owing to the reversible process of self‐assembly of the hexameric capsule. Quenching experiments revealed that the IrIII complex in the capsule was effectively separated from quenchers.
C(sp3)−H Functionalizations Promoted by the Gold Carbene Generated from Vinylidenecyclopropanes
Authors: Li De‐Yao , Fang Wei , Wei Yin , Shi Min 
Published: October 2016

AbstractThe gold carbene generated from vinylidenecyclopropanes (VDCPs) can smoothly perform a C(sp3)−H bond insertion reaction, stereoselectively affording the intramolecular C(sp3)−H bond functionalized product, benzoxepine, with syn‐configuration in moderate to good yields under mild conditions. The KIE investigation on this bond functionalization partially revealed that the carbene insertion step might be rate‐determining. Using a chiral gold(I) catalyst, the first example on the asymmetric variant of gold carbene insertion into C(sp3)−H bond has been disclosed, giving the desired products with excellent results.
Ni3 versus Ni30: A Truncated Octahedron Metal–Organic Cage Constructed with [Ni5(CN)4]6+ Squares and Tripodal Tris‐tacn Ligands That are Large and Flexible
Authors: Zhang Zongyao , Zheng Kunyi , Xia Tianlong , Xu Lijin , Cao Rui 
Published: October 2016

AbstractReactions of trinickel complex of tripodal tris‐tacn ligand N(CH2‐m‐C6H4‐CH2tacn)3 (L, tacn=1,4,7‐triazacyclononane) in acetonitrile–methanol solution with and without phosphate led to two complexes of distinct nuclearities, [(NiIICl)3(CH3OH)3(HPO4)L](PF6) (Ni3, 1) and [(NiII5(CN)4(H2O)8Cl)6L8]Cl30 (Ni30, 2). Ligand L takes upward and downward conformation in the structure of 1 and 2, respectively. It is proposed that phosphate directs the upward conformation of Ni3L to form 1. In the absence of phosphate, Ni3L assembles with cyanide ions, which are formed by Ni‐catalyzed C−CN bond cleavage of acetonitrile, to give a nano‐sized Ni30 cage. Complex 2 represents a discrete truncated octahedron cage assembled with [Ni5(CN)4]6+ squares and large and flexible triangular ligands, which is scarcely observed for self‐assembled metal‐organic cages. The magnetic properties of 1 and 2 were examined, showing intriguing magnetic properties.
ChemInform Abstract: Crystal Structure, 7Li NMR, and Structural Relationship of Two Rare‐Earth Metal Richer Polar Intermetallics: La15Ge9Li1.50(16) and La7Ge3.
Authors: Nam Gnu , Jo Hongil , Ok Kang Min , Kim Jongsik , You Tae‐Soo 
Published: October 2016

AbstractSmall single crystals of La15Ge9Li1.50 (I) and La7Ge3 (II) are obtained by solid state reaction of a 15:9:2 (7:3) molar mixture of the elements (Nb ampoule in evacuated silica tubes, 1080 °C, 5 h).
ChemInform Abstract: One Dimensional Group 12 Metal Undecafluoridoditantalates.
Authors: Tavcar Gasper , Goreshnik Evgeny 
Published: October 2016

AbstractSingle crystals of Cd(Ta2F11)2 and Hg(Ta2F11)2 are grown from solutions of CdF2 or HgF2 and TaF5 in anhydrous HF (crystallization vessel, 28 K temperature gradient, quantitative yield).
ChemInform Abstract: Versatile Route to Benzoannulated Medium‐Ring Carbocycles via Aryne Insertion into Cyclic 1,3‐Diketones: Application to a Synthesis of Radermachol.
Authors: Samineni Ramesh , Srihari Pabbaraja , Mehta Goverdhan 
Published: October 2016

AbstractThe facile procedure allows the synthesis of benzoannulated 7‐ and 8‐membered carbocycles including the Radermachol precursor (IX) from in situ generated arynes and cyclic 1,3‐diketones.
ChemInform Abstract: Mild C—H/C—C Activation by Z‐Selective Cobalt Catalysis.
Authors: Zell Daniel , Bu Qingqing , Feldt Milica , Ackermann Lutz 
Published: October 2016

AbstractThe cobalt‐catalyzed reaction of indoles (I) with vinylcyclopropanes (II) leads to desired 2‐functionalized indoles with moderate to high Z‐selectivity.
ChemInform Abstract: Catalyst‐Free Insertion of Sulfoxonium Ylides into Aryl Thiols. A Direct Preparation of β‐Keto Thioethers.
Authors: Dias Rafael M. P. , Burtoloso Antonio C. B. 
Published: October 2016

AbstractThe presented method is an useful alternative to traditional thioether syntheses that may employ metal catalysts in combination with diazo compounds or toxic and hardly accessible haloketones.
ChemInform Abstract: Facile and Green Chemistry Access to 5‐Aryl‐1,2,4‐triazolidine‐3‐thiones in Aqueous Medium.
Authors: Ramesh Rathinam , Lalitha Appaswami 
Published: October 2016

AbstractA rapid, facile approach is disclosed for the one‐pot, cyclocondensation of aromatic aldehydes with thiosemicarbazides in aqueous ethanol as green solvent leading to aryltriazolidine‐thiones in good yields.
ChemInform Abstract: Redox‐Divergent Hydrogen‐Retentive or Hydrogen‐Releasing Synthesis of 3,4‐Dihydroisoquinolines or Isoquinolines.
Authors: He Ke‐Han , Zhang Wei‐Dong , Yang Ming‐Yu , Tang Kai‐Li , Qu Mengnan , Ding You‐Song , Li Yang 
Published: October 2016

AbstractThe Ru‐catalyzed chemoselective annulation of arylimines (I) to give isoquinolines (II) is developed.
ChemInform Abstract: Chiral Phosphoric Acid‐Catalyzed Enantioselective Formal [3 + 2] Cycloaddition of Azomethine Imines with Enecarbamates.
Authors: Wang Yang , Wang Qian , Zhu Jieping 
Published: October 2016

AbstractA series of isoquinoline‐fused pyrazolidines containing 2 or 3 contiguous stereocenters is obtained with complete regio‐ and diastereoselectivity and excellent enantioselectivity.
ChemInform Abstract: A Convenient Domino Ferrier Rearrangement‐Intramolecular Cyclization for the Synthesis of Novel Benzopyran‐Fused Pyranoquinolines.
Authors: Moshapo Paseka T. , Sokamisa Mokela , Mmutlane Edwin M. , Mampa Richard M. , Kinfe Henok H. 
Published: October 2016

AbstractA one‐pot three‐component cyclocondensation sequence involving the Ferrier and Povarov‐like reactions is presented to synthesize novel pentacyclic N‐heterocycles.
ChemInform Abstract: Synthesis of 6‐Trichloromethylphenanthridines by Transition Metal‐Free Radical Cyclization of 2‐Isocyanobiphenyls.
Authors: Zhou Yuhan , Wu Changpeng , Dong Xiaoliang , Qu Jingping 
Published: October 2016

AbstractFurther transformation of the products to 6‐functionalized phenanthridines is demonstrated.
ChemInform Abstract: Catalytic Asymmetric Synthesis of Phosphoryl‐1,4‐dihydropyridazines via an Enantioselective Allylic Alkylation/1,3‐Dipolar Cycloaddition/Rearrangement Reaction Sequence.
Authors: Du Fei , Yin Liyang , Ning Yanqiang , Peng Yungui 
Published: October 2016

AbstractA novel methodology for the highly enantioselective synthesis of pharmaceutically important phosphorylated pyridazine derivatives is developed.
ChemInform Abstract: Chemistry of Cyclic Imides: An Overview on the Past, Present and Future
Authors: Kavitha Kankanala , Shanthi Praveena Koduru Sri , Venkat Shivaji Ramarao Edupuganti Veera , Sreenivasa Murthy Nandula Yadagiri , Pal Sarbani 
Published: October 2016

AbstractReview: data on synthesis and reactions of cyclic imides mainly from 1980 to the end f 2015
ChemInform Abstract: Perovskite Materials for Light‐Emitting Diodes and Lasers
Authors: Veldhuis Sjoerd A. , Boix Pablo P. , Yantara Natalia , Li Mingjie , Sum Tze Chien , Mathews Nripan , Mhaisalkar Subodh G. 
Published: October 2016

AbstractReview: 152 refs.
Neonikotinoide schaden Honigbienen
Authors: Wessler Ignaz 
Published: October 2016

AbstractSchon länger stehen Neonikotinoide im Verdacht, eine mögliche Ursache für das seit Jahren zu beobachtende Bienensterben zu sein [4]. Nun wurde ein neuer Mechanismus entdeckt, nach dem die Insektizide über den Futtersaft der Bienen auf die Larven wirken.