bluuebunny/crossref_metadata_2025_split huggingface dataset:
Mechanical thrombectomy for emergent large vessel occlusion: a critical appraisal of recent randomized controlled clinical trials
Authors: Tsivgoulis Georgios , Safouris Apostolos , Katsanos Aristeidis H. , Arthur Adam S. , Alexandrov Andrei V. 
Published: January 2016

AbstractBackground and PurposeAfter numerous attempts to prove efficacy for endovascular treatment of ischemic stroke, a series of recent randomized controlled clinical trials (RCTs) established fast mechanical thrombectomy (MT) as a safe and effective novel treatment for emergent large vessel occlusion (ELVO) in the anterior cerebral circulation.MethodsWe reviewed five recent RCTs that evaluated the safety and efficacy of MT in ELVO patients and captured available information on recanalization/reperfusion, symptomatic intracranial hemorrhage (sICH), clinical outcome, and mortality. MT was performed with stent retrievers, aspiration techniques, or a combination of these endovascular approaches. We applied meta‐analytical methodology to evaluate the pooled effect of MT on recanalization/reperfusion, sICH, functional independence (modified Rankin scale score of 0–2) and 3‐month mortality rates in comparison to best medical therapy (BMT).ResultsMT was associated with increased likelihood of complete recanalization/reperfusion (RR: 2.22; 95%CI: 1.89–2.62; P < 0.00001) and 3‐month functional independence (RR: 1.72; 95%CI: 1.48–1.99; P < 0.00001) without any heterogeneity across trials (I2 = 0%). The absolute benefit increase in MT for complete recanalization/reperfusion and functional independence was 44 (NNT = 2) and 16 (NNT = 6), respectively. MT was not associated with increased risk of 3‐month mortality (15% with MT vs. 19% with BMT) and sICH (4.6% with MT vs. 4.3% with BMT), while small heterogeneity was detected across the included trials (I2 < 25%).ConclusionsMT is a safe and highly effective treatment for patients with ELVO in the anterior circulation. For every six ELVO patients treated with MT three more will achieve complete recanalization at 24 h following symptom onset and one more will be functionally independent at 3 months in comparison to BMT.
Anticancer efficacy of the hypoxia‐activated prodrug evofosfamide (TH‐302) in osteolytic breast cancer murine models
Authors: Liapis Vasilios , Zinonos Irene , Labrinidis Agatha , Hay Shelley , Ponomarev Vladimir , Panagopoulos Vasilios , Zysk Aneta , DeNichilo Mark , Ingman Wendy , Atkins Gerald J. , Findlay David M. , Zannettino Andrew C. W. , Evdokiou Andreas 
Published: January 2016

AbstractTumor hypoxia is a major cause of treatment failure for a variety of malignancies. However, hypoxia offers treatment opportunities, exemplified by the development of compounds that target hypoxic regions within tumors. Evofosfamide (TH‐302) is a prodrug created by the conjugation of 2‐nitroimidazole to bromo‐isophosphoramide mustard (Br‐IPM). When evofosfamide is delivered to hypoxic regions, the DNA cross‐linking effector, Br‐IPM, is released. This study assessed the cytotoxic activity of evofosfamide in vitro and its antitumor activity against osteolytic breast cancer either alone or in combination with paclitaxel in vivo. A panel of human breast cancer cell lines were treated with evofosfamide under hypoxia and assessed for cell viability. Osteolytic MDA‐MB‐231‐TXSA cells were transplanted into the mammary fat pad, or into tibiae of mice, allowed to establish and treated with evofosfamide, paclitaxel, or both. Tumor burden was monitored using bioluminescence, and cancer‐induced bone destruction was measured using micro‐CT. In vitro, evofosfamide was selectively cytotoxic under hypoxic conditions. In vivo evofosfamide was tumor suppressive as a single agent and cooperated with paclitaxel to reduce mammary tumor growth. Breast cancer cells transplanted into the tibiae of mice developed osteolytic lesions. In contrast, treatment with evofosfamide or paclitaxel resulted in a significant delay in tumor growth and an overall reduction in tumor burden in bone, whereas combined treatment resulted in a significantly greater reduction in tumor burden in the tibia of mice. Evofosfamide cooperates with paclitaxel and exhibits potent tumor suppressive activity against breast cancer growth in the mammary gland and in bone.
Influence of Pre‐organised Architecture on Cell Adhesion by Using Multivalent RGD Compounds
Authors: Grassin Adrien , Jourdan Muriel , Dumy Pascal , Boturyn Didier 
Published: January 2016

AbstractMultimeric RGD‐containing compounds were designed to study the influence of ligand architecture on binding avidity. We report the synthesis of a series of tetrameric RGD compounds and their in vitro biological evaluation. The further application of molecular dynamic simulations for structural studies of RGD derivatives reveals that the observed affinities correlate with the accessibility of segregated RGD motif.
Characterization of the Shigella and Salmonella Type III Secretion System Tip–Translocon Protein–Protein Interaction by Paramagnetic Relaxation Enhancement
Authors: Kaur Kawaljit , Chatterjee Srirupa , De Guzman Roberto N. 
Published: January 2016

AbstractMany Gram‐negative pathogens, such as Shigella and Salmonella, assemble the type III secretion system (T3SS) to inject virulence proteins directly into eukaryotic cells to initiate infectious diseases. The needle apparatus of the T3SS consists of a base, an extracellular needle, a tip protein complex, and a translocon. The atomic structure of the assembled tip complex and the translocon is unknown. Here, we show by NMR paramagnetic relaxation enhancement (PRE) that the mixed α–β domain at the distal region of the Shigella and Salmonella tip proteins interacts with the N‐terminal ectodomain of their major translocon proteins. Our results reveal the binding surfaces involved in the tip–translocon protein–protein interaction and provide insights about the assembly of the needle apparatus of the T3SS.
A Bis(guanidinium)alcohol Attached to a Hairpin Polyamide: Synthesis, DNA Binding, and Plasmid Cleavage
Authors: Wirth‐Hamdoune Daniela , Ullrich Stefan , Scheffer Ute , Radanović Toni , Dürner Gerd , Göbel Michael W. 
Published: January 2016

AbstractBis(guanidinium)alcohols have been designed to react with phosphodiester substrates in a fast transphosphorylation step, a quasi‐intramolecular process taking place in contact ion pairs. Here the attachment of such compounds to Dervan‐type hairpin polyamides is described. The resulting conjugate 1 binds to AT‐rich DNA duplexes with affinity similar to that of the parent polyamide as shown by UV melting experiments and CD titrations. Conjugate 1 nicks plasmid DNA at concentrations ranging from micromolar to high nanomolar.
Juxta‐terminal Helix Unwinding as a Stabilizing Factor to Modulate the Dynamics of Transmembrane Helices
Authors: Mortazavi Armin , Rajagopalan Venkatesan , Sparks Kelsey A. , Greathouse Denise V. , Koeppe Roger E. 
Published: January 2016

AbstractTransmembrane helices of integral membrane proteins often are flanked by interfacial aromatic residues that can serve as anchors to aid the stabilization of a tilted transmembrane orientation. Yet, physical factors that govern the orientation or dynamic averaging of individual transmembrane helices are not well understood and have not been adequately explained. Using solid‐state 2H NMR spectroscopy to examine lipid bilayer‐incorporated model peptides of the GWALP23 (acetyl‐GGALW(LA)6LWLAGA‐amide) family, we observed substantial unwinding at the terminals of several tilted helices spanning the membranes of DLPC, DMPC, or DOPC lipid bilayers. The fraying of helix ends might be vital for defining the dynamics and orientations of transmembrane helices in lipid bilayer membranes.
Aliphatic Halogenase Enables Late‐Stage C−H Functionalization: Selective Synthesis of a Brominated Fischerindole Alkaloid with Enhanced Antibacterial Activity
Authors: Zhu Qin , Hillwig Matthew L. , Doi Yohei , Liu Xinyu 
Published: January 2016

AbstractThe anion promiscuity of a newly discovered standalone aliphatic halogenase WelO5 was probed and enabled the selective synthesis of 13R‐bromo‐12‐epi‐fischerindole U via late‐stage enzymatic functionalization of an unactivated sp3 C−H bond. Pre‐saturating the WelO5 active site with a non‐native bromide anion was found to be critical to the highly selective in vitro transfer of bromine, instead of chlorine, to the target carbon center and also allowed the relative binding affinity of bromide and chloride towards the WelO5 enzyme to be assessed. This study further revealed the critical importance of halogen substitution on modulating the antibiotic activity of fischerindole alkaloids and highlights the promise of WelO5‐type aliphatic halogenases as enzymatic tools to fine‐tune the bioactivity of complex natural products.
Phospha‐Michael Addition as a New Click Reaction for Protein Functionalization
Authors: Lee Yan‐Jiun , Kurra Yadagiri , Liu Wenshe R. 
Published: January 2016

AbstractA new type of click reaction between an alkyl phosphine and acrylamide was developed and applied for site‐specific protein labeling in vitro and in live cells. Acrylamide is a small electrophilic olefin that readily undergoes phospha‐Michael addition with an alkyl phosphine. Our kinetic study indicated a second‐order rate constant of 0.07 m−1 s−1 for the reaction between tris(2‐carboxyethyl)phosphine and acrylamide at pH 7.4. To demonstrate its application in protein functionalization, we used a dansyl–phosphine conjugate to successfully label proteins that were site‐specifically installed with Nɛ‐acryloyl‐l‐lysine and employed a biotin–phosphine conjugate to selectively probe human proteins that were metabolically labeled with N‐acryloyl‐galactosamine.
Successful outcome following detection and removal of a very small ovarian teratoma associated with anti‐NMDA receptor encephalitis during pregnancy
Authors: Mizutamari Etsuko , Matsuo Yuji , Namimoto Tomohiro , Ohba Takashi , Yamashita Yasuyuki , Katabuchi Hidetaka 
Published: January 2016

Key Clinical MessageAn important part of anti–N‐methyl‐d‐aspartate (NMDA) receptor encephalitis treatment is prompt detection and removal of any associated ovarian teratoma, regardless of size. High‐resolution transvaginal ultrasonography followed by targeted CT with adaptive iterative dose reduction (AIDR) is a useful strategy for distinguishing small ovarian teratomas from luteal cysts during pregnancy.
A case of lethal giant inguinal hernia
Authors: Chida Yasuyuki , Inokuchi Ryota , Kumada Yoshibumi , Shinohara Kazuaki 
Published: January 2016

Key Clinical MessageSeveral elective surgical managements have been reported regarding giant inguinal hernias (GIH), but no case of death. We here present a fatal case of bilateral GIHs in an extremely obese man with dyspnea. Bilateral GIHs are difficult to recognize in extreme obesity. Moreover, operation is recommended when GIH is diagnosed.
Design Strategies for a Denitrification Catalyst with Improved Resistance against Alkali Poisoning: The Significance of Nanoconfining Spaces and Acid–Base Balance
Authors: Wang Penglu , Wang Haiqiang , Chen Xiongbo , Wu Zhongbiao 
Published: January 2016

AbstractBased on the ideas of the nanoconfining effect and the acid–base balance mechanism, a dual‐protection strategy was designed to solve the deactivation problem that occurs on ceria‐based deNOx catalysts. The nanoconfining spaces were provided by multilayer titanate nanotubes, and the acid–base balance was guaranteed by the modification of sulfuric acid pickling on titanate nanotubes. The ceria‐doped 0.1 mol L−1 sulfated titanate nanotubes catalyst exhibited an excellent selective catalytic reduction (SCR) catalytic activity and enhanced alkali resistance. It was found that the enhanced alkali resistance was relevant for the perfect hollow‐tubular structure, repeatable Ce4+/Ce3+ redox cycles, and increased surface acid sites. In situ diffuse reflectance infrared Fourier transform spectroscopy further identified that the balance of acidity and basicity on K‐Ce/0.1STNTs ensured the activity of adsorbed NH3 and NOx species. The SCR reaction was thus facilitated over the sulfated catalysts and both the Eley–Rideal and Langmuir–Hinshelwood mechanisms may occur during the reaction.
Application of Pd Nanoparticles Supported on Mesoporous Hollow Silica Nanospheres for the Efficient and Selective Semihydrogenation of Alkynes
Authors: Verho Oscar , Zheng Haoquan , Gustafson Karl P. J. , Nagendiran Anuja , Zou Xiaodong , Bäckvall Jan‐E. 
Published: January 2016

AbstractHerein, the preparation of a heterogeneous catalyst consisting of 1–2 nm sized Pd nanoparticles supported on amino‐functionalized mesoporous hollow silica nanospheres and its use for the semihydrogenation of mono‐ and disubstituted alkynes is reported. By utilizing this Pd nanocatalyst together with the green poisoning agent DMSO, high yields of the desired alkenes could be achieved, while suppressing the degree of over‐reduction to alkanes. To our delight, the Pd nanocatalyst displayed remarkable chemoselectivity towards the alkyne moiety, allowing the transformation to be carried out in the presence of other reducible functionalities, such as halogens, carbonyl, and nitro groups.
Surface Reconstruction of Facet‐Functionalized SrTiO3 Nanocrystals for Photocatalytic Hydrogen Evolution
Authors: Wang Bin , Shen Shaohua , Guo Liejin 
Published: January 2016

AbstractThe surface structure determines the surface electronic and chemical properties of semiconducting nanocrystals for efficient photocatalysis. Herein, SrTiO3 nanocrystals enclosed by {0 0 1} and {0 2 3} facets functionalized for photoreduction and photooxidation, respectively, were surface‐reconstructed with a disordered overlayer created by a thermal hydrogenation process. These surface‐reconstructed SrTiO3 nanocrystals showed much higher photocatalytic activities than the pristine SrTiO3, which was attributed to the enhanced charge transfer ability and accelerated oxidative reaction kinetics induced by the oxygen vacancies in disordered overlayer. Given the maintained {0 0 1} and {0 2 3} facets ensuring spatial charge separation and functioning for reduction and oxidation reactions, respectively, the surface‐reconstructed SrTiO3 nanocrystals enclosed with {0 2 3} and {0 0 1} facets in appropriate ratio showed the highest photocatalytic activity for hydrogen evolution.
Electrochemical Reduction of Carbon Dioxide at Gold‐Palladium Core–Shell Nanoparticles: Product Distribution versus Shell Thickness
Authors: Humphrey Jo J. L. , Plana Daniela , Celorrio Verónica , Sadasivan Sajanikumari , Tooze Robert P. , Rodríguez Paramaconi , Fermín David J. 
Published: January 2016

AbstractThe electrocatalytic reduction of CO2 at carbon‐supported Au‐Pd core–shell nanoparticles is investigated systematically as a function of the Pd shell thickness. Liquid‐ and gas‐phase products were determined by off‐line 1H NMR spectroscopy and on‐line electrochemical mass spectrometry. Our results uncover the relationship between the nature of the products generated and the Pd shell thickness. CO and H2 are the only products generated at 1 nm thick shells, whereas shells of 5 and 10 nm produced HCOO−, CH4 and C2H6. The concentration of HCOO− detected in the electrolyte was dependent on the applied potential and reached a maximum Faradaic efficiency of 27 % at −0.5 V versus the reversible hydrogen electrode for 10 nm thick shells. We conclude that collisions between absorbed hydrogen at relaxed Pd lattices and strongly bound “CO‐like” intermediates promote the complete hydrogenation to C1 and C2 alkanes without the generation of other products, such as alcohols and aldehydes.
Electrodeposition of Stoichiometric Indium Antimonide from Room‐Temperature Ionic Liquid 1‐Butyl‐1‐Methylpyrrolidinium Dicyanamide
Authors: Hsieh Yi‐Ting , Chen Yu‐Chen , Sun I‐Wen 
Published: January 2016

AbstractA stoichiometric InSb film was electrodeposited on a nickel (Ni) substrate in a room‐temperature ionic liquid, 1‐butyl‐1‐methylpyrrolidinium dicyanamide (BMP‐DCA), containing anhydrous InCl3 and SbCl3 with a molar concentration ratio of 1:1. The composition of the deposited InSb film was found to depend on both the applied potential and the deposition charge. Crystalline deposits can be directly obtained at low temperature (60 °C) without any post‐heat treatment. The optical band gap of the InSb film analyzed by using FTIR spectroscopy measurements was approximately 0.17 eV. Results from photocurrent experiments indicate that the electrodeposited InSb film was a p‐type semiconductor.
Principles of Bipolar Electrochemistry
Authors: Crooks Richard M. 
Published: January 2016

AbstractThis is a tutorial on the basic concepts underlying bipolar electrochemistry. It is intended as an accompaniment to ChemElectroChem’s special issue on this topic. The guest editors of this special issue think it is worthwhile to introduce bipolar electrochemistry to a broader (electrochemistry) audience by explaining the similarities and differences between bipolar electrochemistry and normal electrochemical methods. The work presented herein has been adapted from: S. E. Fosdick, K. N. Knust; K. Scida; R. M. Crooks “Bipolar Electrochemistry” Angew. Chem. Int. Ed. 2013, 52, 10438–10456 (DOI: 10.1002/anie.201300947); “Bipolare Elektrochemie” Angew. Chem. 2013, 125, 10632–10651 (DOI: 10.1002/ange.201300947).
Molecularly Dispersed Donors in Acceptor Molecular Crystals for Photon Upconversion under Low Excitation Intensity
Authors: Hosoyamada Masanori , Yanai Nobuhiro , Ogawa Taku , Kimizuka Nobuo 
Published: January 2016

AbstractFor real‐world applications of photon upconversion based on the triplet–triplet annihilation (TTA‐UC), it is imperative to develop solid‐state TTA‐UC systems that work effectively under low excitation power comparable to solar irradiance. As an approach in this direction, aromatic crystals showing high triplet diffusivity are expected to serve as a useful platform. However, donor molecules inevitably tend to segregate from the host acceptor crystals, and this inhomogeneity results in the disappointing performance of crystalline state TTA‐UC. In this work, a series of cast‐film‐forming acceptors was developed, which provide both regular acceptor alignment and soft domains of alkyl chains that accommodate donor molecules without segregation. A typical triplet sensitizer, PtII octaethylporphyrin (PtOEP), was dispersed in these acceptor crystals without aggregation. As a result, efficient triplet energy transfer from the donor to the acceptor and diffusion of triplet excitons among regularly aligned anthracene chromophores occurred. It resulted in TTA‐UC emission at low excitation intensities, comparable to solar irradiance.
Studies of a Large Odd‐Numbered Odd‐Electron Metal Ring: Inelastic Neutron Scattering and Muon Spin Relaxation Spectroscopy of Cr8Mn
Authors: Baker Michael L. , Lancaster Tom , Chiesa Alessandro , Amoretti Giuseppe , Baker Peter J. , Barker Claire , Blundell Stephen J. , Carretta Stefano , Collison David , Güdel Hans U. , Guidi Tatiana , McInnes Eric J. L. , Möller Johannes S. , Mutka Hannu , Ollivier Jacques , Pratt Francis L. , Santini Paolo , Tuna Floriana , Tregenna‐Piggott Philip L. W. , Vitorica‐Yrezabal Iñigo J. , Timco Grigore A. , Winpenny Richard E. P. 
Published: January 2016

AbstractThe spin dynamics of Cr8Mn, a nine‐membered antiferromagnetic (AF) molecular nanomagnet, are investigated. Cr8Mn is a rare example of a large odd‐membered AF ring, and has an odd‐number of 3d‐electrons present. Odd‐membered AF rings are unusual and of interest due to the presence of competing exchange interactions that result in frustrated‐spin ground states. The chemical synthesis and structures of two Cr8Mn variants that differ only in their crystal packing are reported. Evidence of spin frustration is investigated by inelastic neutron scattering (INS) and muon spin relaxation spectroscopy (μSR). From INS studies we accurately determine an appropriate microscopic spin Hamiltonian and we show that μSR is sensitive to the ground‐spin‐state crossing from S=1/2 to S=3/2 in Cr8Mn. The estimated width of the muon asymmetry resonance is consistent with the presence of an avoided crossing. The investigation of the internal spin structure of the ground state, through the analysis of spin‐pair correlations and scalar‐spin chirality, shows a non‐collinear spin structure that fluctuates between non‐planar states of opposite chiralities.
A Study on the Photoreaction of 2(5H)‐Furanones with Substituted Acetylenes: Evidence for a Mechanistic Reformulation
Authors: Flores Ramon , Font Josep , Alibés Ramon , Figueredo Marta 
Published: January 2016

AbstractThe photoreaction of 2(5H)‐furanones with alkynes has been investigated. The complexity of this process is evidenced by the variety of isolated products, which have allowed disclosing interesting mechanistic aspects. When the reaction is performed in acetonitrile under direct excitation, in addition to the primary [2+2] cycloadducts, products derived from an 1,3‐acyl shift rearrangement are also formed. For unsymmetrical alkynes, the rearrangement of the head‐to‐tail primary adducts produces new regioisomers and, when the starting furanone is chiral, this rearrangement inverts the relative anti/syn geometry of the primary cycloadducts. In the reactions performed in acetone under photosensitized conditions, rearranged products were never detected, supporting that the 1,3‐acyl shift takes place from the singlet excited state S1 of the β,γ‐unsaturated lactone. When bis(trimethylsilyl)acetylene is used as the alkyne partner, the major photoproducts are monocyclic bis(trimethylsilyl)lactones.
Ring Opening of a meso‐Triaryl 25‐Oxasmaragdyrin Macrocycle by m‐Chloroperoxybenzoic Acid
Authors: Kalita Hemanta , Ghosh Avijit , Lee Way‐Zen , Ravikanth Mangalampalli 
Published: January 2016

AbstractSmaragdyrin, a class of expanded porphyrin macrocycles, upon treatment with meta‐chloroperoxybenzoic acid (mCPBA) underwent oxidative ring opening to form an unprecedented linear pentaheterocyclic compound. The linear pentaheterocyclic compound was freely soluble in common organic solvents and characterized in detail by HRMS, 1D and 2D NMR spectroscopy, and X‐ray crystallography. Our preliminary studies indicated that the linear pentaheterocyclic compound can specifically sense anions such as H2PO4− and CN− ions, which was corroborated by absorption and fluorescence studies.
Metal‐Ligand Cooperativity in a Methandiide‐Derived Iridium Carbene Complex
Authors: Weismann Julia , Waterman Rory , Gessner Viktoria H. 
Published: January 2016

AbstractThe synthesis, electronic structure, and reactivity of the first Group 9 carbene complex, [Cp*IrL] [L=C(Ph2PS)(SO2Ph)] (2), based on a dilithio methandiide are reported. Spectroscopic as well as computational studies have shown that, despite using a late transition‐metal precursor, sufficient charge transfer occurred from the methandiide to the metal, resulting in a stable, nucleophilic carbene species with pronounced metal‐carbon double‐bond character. The potential of this iridium complex in the activation of a series of E−H bonds by means of metal‐ligand cooperation has been tested. These studies have revealed distinct differences in the reactivity of 2 compared to a previously reported ruthenium analogue. Whereas attempts to activate the O−H bond in different phenol derivatives resulted in ligand cleavage, H−H and Si−H activation as well as dehydrogenation of isopropanol have been accomplished. These reactions are driven by the transformation of the carbene to an alkyl ligand. Contrary to a previously reported ruthenium carbene system, the dihydrogen activation has been found to proceed by a stepwise mechanism, with the activation first taking place solely at the metal. The activated products further reacted to afford a cyclometalated complex through liberation of the activated substrates. In the case of triphenylsilane, cyclometalation could thus be induced by a substoichiometric (i.e., catalytic) amount of silane.