bluuebunny/crossref_metadata_2025_split huggingface dataset:
Surgical cutdown versus percutaneous access in transfemoral transcatheter aortic valve implantation: Insights from the Brazilian TAVI registry
Authors: Bernardi Fernando L.M. , Gomes Wilton F. , de Brito Fabio S. , Mangione Jose A. , Sarmento‐Leite Rogério , Siqueira Dimitry , Carvalho Luiz A. , Tumelero Rogério , Guerios Enio E. , Lemos Pedro A. 
Published: January 2015

ObjectiveTo compare the 1‐year outcomes of complete percutaneous approach versus surgical vascular approach for transfemoral transcatheter aortic valve implantation (TAVI), among “real‐world” patients from the multi‐center Brazilian TAVI registry.BackgroundVascular access still remains a major challenge for TAVI via transfemoral approach. Vascular access through complete percutaneous approaches or through open surgical vascular techniques seems to be acutely similar. However, the long‐term outcomes of both techniques remain poorly described.MethodsThe study population comprised all patients treated via transfemoral route in the Brazilian TAVI registry, a “real‐world”, nation‐based, multi‐center study. Patients were divided according to the initial vascular access approach (percutaneous vs. surgical) and clinically followed‐up for 1 year. The primary endpoint was the incidence of combined adverse events all‐cause mortality, life‐threatening bleeding, and/or major vascular complication at 1 year.ResultsA total of 402 patients from 18 centers comprised the study population (percutaneous approach in 182 patients; surgical cutdown approach 220 patients). The incidence of combined adverse events was not different in the percutaneous and the surgical groups at 30 days (17.6% vs. 16.3%; P = 0.8) and at 1 year (primary endpoint) (30.9% vs. 28.8%; P = 0.8). Also, the study groups overall were comparable regarding the incidence of each individual safety adverse events at 30 days and at 1 year.ConclusionTotal percutaneous techniques or surgical cutdown and closure may provide similar safety and effectiveness during the first year of follow‐up in patients undergoing transfemoral TAVI. © 2015 Wiley Periodicals, Inc.
Structural Investigation of the High Spin→Low Spin Relaxation Dynamics of the Porous Coordination Network [Fe(pz)Pt(CN)4]⋅2.6 H2O
Authors: Delgado Teresa , Tissot Antoine , Besnard Céline , Guénée Laure , Pattison Philip , Hauser Andreas 
Published: January 2015

AbstractThe Hoffman‐type coordination compound [Fe(pz)Pt(CN)4]⋅2.6 H2O (pz=pyrazine) shows a cooperative thermal spin transition at around 270 K. Synchrotron powder X‐Ray diffraction studies reveal that a quantitative photoinduced conversion from the low‐spin (LS) state into the high‐spin (HS) state, based on the light‐induced excited spin‐state trapping effect, can be achieved at 10 K in a microcrystalline powder. Time‐resolved measurements evidence that the HS→LS relaxation proceeds by a two‐step mechanism: a random HS→LS conversion at the beginning of the relaxation is followed by a nucleation and growth process, which proceeds until a quantitative HS→LS transformation has been reached.
The Fate of NHC‐Stabilized Dicarbon
Authors: Georgiou Dayne C. , Stringer Bradley D. , Hogan Conor F. , Barnard Peter J. , Wilson David J. D. , Holzmann Nicole , Frenking Gernot , Dutton Jason L. 
Published: January 2015

AbstractThe attempted synthesis of NHC‐stabilized dicarbon (NHCCCNHC) through deprotonation of a doubly protonated precursor ([NHCCHCHNHC]2+) is reported. Rather than deprotonation, a clean reduction to NHCCHCHNHC is observed with a variety of bases. The apparent resistance towards deprotonation to the target compound led to a reinvestigation of the electronic structure of NHC→CC←NHC, which showed that the highest occupied molecular orbital/lowest unoccupied molecular orbital (HOMO/LUMO) gap is likely too small to allow for isolation of this species. This is in contrast to the recent isolation of the cyclic alkylaminocarbene analogue (cAACCCcAAC), which has a large HOMO–LUMO gap. A detailed theoretical study illuminates the differences in electronic structures between these molecules, highlighting another case of the potential advantages of using cAAC rather than NHC as a ligand. The bonding analysis suggests that the dicarbon compounds are well represented in terms of donor–acceptor interactions L→C2←L (L=NHC, cAAC).
Mesoporous Alumina from Colloidal Biotemplating of Al Clusters
Authors: Sachse Alexander , Cardoso Laura , Kostov Krassimir L. , Gérardin Corine , Belamie Emmanuel , Alonso Bruno 
Published: January 2015

AbstractA simple and green synthesis route was disclosed for the achievement of mesoporous alumina microparticles employing polysaccharide nanoparticles (α‐chitin nanorods) as templates. Pore textures can be tuned by the cationic alumina precursor. Compared to small cations, the use of Al13 and Al30 oxo‐hydroxo clusters leads to better defined and elongated mesopores. Electron microscopy and spectroscopic (13C, 27Al NMR, XPS) measurements demonstrated that this is related to the effective coating of α‐chitin nanorods by these pre‐condensed colloids.
DFT Study of the Molybdenum‐Catalyzed Deoxydehydration of Vicinal Diols
Authors: Lupp Daniel , Christensen Niels Johan , Dethlefsen Johannes R. , Fristrup Peter 
Published: January 2015

AbstractThe mechanism of the molybdenum‐catalyzed deoxydehydration (DODH) of vicinal diols has been investigated using density functional theory. The proposed catalytic cycle involves condensation of the diol with an MoVI oxo complex, oxidative cleavage of the diol resulting in an MoIV complex, and extrusion of the alkene. We have compared the proposed pathway with several alternatives, and the results have been corroborated by comparison with the molybdenum‐catalyzed sulfoxide reduction recently published by Sanz et al. and with experimental observations for the DODH itself. Improved understanding of the mechanism should expedite future optimization of molybdenum‐catalyzed biomass transformations.
Robustness Screen in Enantioselective Catalysis Enabled Generation of Enantioenriched Heterocyclic Scaffolds in One Pot
Authors: Bagle Pradip N. , Shinde Valmik S. , Patil Nitin T. 
Published: January 2015

AbstractEnantioselective catalysis has emerged as a powerful synthetic paradigm and has accelerated the development of new methods to make diverse chiral molecules. Generally, these reactions are very sensitive to the steric and electronic environment present in the catalyst as well as the substrates. With this scenario, the presence of an additional component in the reaction mixture is expected to add complexity in achieving the enantioselective variants. Herein, we report that various enantioenriched molecules could be obtained from multiple starting materials in one pot. The reaction of aminoaromatics A with alkynols B1, B2, B3…︁Bn with a AuI/chiral Brønsted acid catalyst afforded AB1*, AB2*, AB3*…ABn*; while, the reaction of alkynols B with aminoaromatics A1, A2, A3…An under the same reaction conditions gave A1B*, A2B*, A3B*…AnB*.
RhII‐Catalyzed [3+2] Cycloaddition of 2 H‐Azirines with N‐Sulfonyl‐1,2,3‐Triazoles
Authors: Zhao Yun‐Zhou , Yang Hai‐Bin , Tang Xiang‐Ying , Shi Min 
Published: January 2015

AbstractRhII‐catalyzed intermolecular [3+2] cycloaddition of 2 H‐azirines with N‐sulfonyl‐1,2,3‐triazoles is disclosed, in which a series of fully functionalized pyrroles is produced via rhodium azavinyl carbene intermediates. A distinct feature of this reaction is that the azavinyl carbene serves as a [2 C] equivalent, instead of as [1 C] or aza‐[3 C] synthons, which have been reported previously in cyclopropanations and [3+n] cycloadditions. Moreover, this methodology has also been successfully applied in the total synthesis of URB447 as well as the formal synthesis of Atorvastatin (Lipitor).
Synthesis of Coumarin‐Pillar[5]arene as a Selective Fluorescent Probe for Methyl‐Parathion
Authors: Zhang Fan , Cao Xianliang , Tian Demei , Li Haibing 
Published: January 2015

AbstractA novel coumarin‐pillar[5]arene derivative (P5C10) was prepared. Fluorescence spectroscopy indicates that P5C10 shows good selectivity towards methyl‐parathion. A combination of NMR spectra, MALDI‐TOF spectra and computational calculations reveals the formation of a host‐guest complex driven by π‐π stacking interactions.
Influence of Metallic Modification on Ethylbenzene Dealkylation over ZSM‐5 Zeolites
Authors: Hu Chao , Li Junhui , Jia Wenzhi , Liu Min , Hao Zhixian , Zhu Zhirong 
Published: January 2015

AbstractA series of metal‐modified HZSM‐5 catalysts were prepared by impregnation and were used for ethylbenzene dealkylation of the mixed C8 aromatics (ethylbenzene, m‐xylene and o‐xylene). The effects of different supported metals (Pt, Pd, Ni, Mo) on catalytic performance, including reaction conditions, were investigated. The physicochemical properties of catalysts were characterized by means of XRD, BET, TEM and NH3‐TPD. Experimental results showed that metallic modification obviously increased the ethylbenzene conversion and reduced the coke deposition, greatly improving the catalyst stability. The distinction of ethylbenzene conversion depended on the interaction between hydrogenation reactivity and acidic cracking of bifunctional metal‐modified zeolites. Compared with Pt and Ni, Pd and Mo were easier to disperse into HZSM‐5 micropores during loading metals. The acidic density of different metal‐modified HZSM‐5 declined in the following order: HZSM‐5>Pt/HZSM‐5>Pd/HZSM‐5>Ni/HZSM‐5>Mo/HZSM‐5. The activity of ethylene hydrogenation decreased with Pt/HZSM‐5>Pd/HZSM‐5>Ni/HZSM‐5>Mo/HZSM‐5. In comparison, Pd/HZSM‐5 showed the best catalytic performance with both high activity and high selectivity, with less cracking loss of m‐xylene and o‐xylene. Moreover, the following reaction conditions were found to be preferable for ethylbenzene dealkylation over Pd/HZSM‐5: 340°C, 1.5 MPa H2, WHSV 4 h−1, H2/C8 4 mol/mol.
Four Pillar[5]arene Constitutional Isomers: Synthesis, Crystal Structures, and Host‐Guest Complexation of Their Derivatives with Paraquat in Water
Authors: Zhou Yujuan , Yao Yong , Huang Feihe 
Published: January 2015

AbstractA pillar[5]arene prepared from monomer 1 has four constitutional isomers. Although these constitutional isomers have the same molecular formula, their other properties that we have investigated are more or less different. They have different melting points, different NMR spectra and different crystal structures. Furthermore, the corresponding four anionic constitutional pillar[5]arene isomers derived from these four constitutional isomers showed different binding abilities with paraquat G in water. The association constants of 3a⊃G, 3b⊃G, 3c⊃G and 3d⊃G were determined to be (3.33±0.46)×104 L·mol−1, (5.00±0.63)×104 L·mol−1, (3.33±0.28)×104 L·mol−1, and (1.43±0.09)×104 L·mol−1, respectively.
Characterizing Major Bleeding in Patients With Nonvalvular Atrial Fibrillation: A Pharmacovigilance Study of 27 467 Patients Taking Rivaroxaban
Authors: Tamayo Sally , Frank Peacock W. , Patel Manesh , Sicignano Nicholas , Hopf Kathleen P. , Fields Larry E. , Sarich Troy , Wu Shujian , Yannicelli Daniel , Yuan Zhong 
Published: January 2015

ABSTRACTBackgroundIn nonvalvular atrial fibrillation (NVAF), rivaroxaban is used to prevent stroke and systemic embolism.ObjectiveTo evaluate major bleeding (MB) in NVAF patients treated with rivaroxaban in a real‐world clinical setting.MethodsFrom January 1, 2013, to March 31, 2014, US Department of Defense electronic health care records were queried to describe MB rates and demographics. Major bleeding was identified using a validated algorithm.ResultsOf 27 467 patients receiving rivaroxaban, 496 MB events occurred in 478 patients, an incidence of 2.86 per 100 person‐years (95% confidence interval: 2.61‐3.13). The MB patients were older, mean (SD) age of 78.4 (7.7) vs 75.7 (9.7) years, compared with non‐MB patients. Patients with MB had higher rates of hypertension (95.6% vs 75.8%), coronary artery disease (64.2% vs 36.7%), heart failure (48.5% vs 23.7%), and renal disease (38.7% vs 16.7%). Of MB patients, 63.2% were taking 20 mg, 32.2% 15 mg, and 4.6% 10 mg of rivaroxaban. Four percent of MB patients took warfarin within the prior 30 days. Major bleeding was most commonly gastrointestinal (88.5%) or intracranial (7.5%). Although 46.7% of MB patients received a transfusion, none had sufficient evidence of receiving any type of clotting factor. Fourteen died during their MB hospitalization, yielding a fatal bleeding incidence rate of 0.08 per 100 person‐years (95% confidence interval: 0.05‐0.14). Mean age at death was 82.4 years.ConclusionsIn this large observational study, the MB rate was generally consistent with the registration trial results, and fatal bleeds were rare.
Relationship of light scatter change and Cdc42‐regulated actin status
Authors: Hong Lin , Chavez Stephanie , Smagley Yelena , Chigaev Alexandre , Sklar Larry A. 
Published: January 2015

BackgroundCdc42 GTPase has important roles in regulating intracellular actin reorganization. The current methods to monitor actin changes are typically complex and point by point.MethodsThe effects of Cdc42 inhibitors on the side scatter changes were tested in a newly developed continuous assay using the flow cytometer. Staining with fluorescently labeled phalloidin was used for comparison.ResultsCdc42‐specific inhibitors caused dose‐dependent changes of both the right‐angle side scatter and the phalloidin‐stained actin.ConclusionsThe right‐angle light scatter change can be used as a method to circumvent phalloidin staining and be an early convenient step in screening Cdc42 inhibitors. © 2015 International Clinical Cytometry Society
Assessing the phylogeographic history of the montane caddisfly Thremma gallicum using mitochondrial and restriction‐site‐associated DNA (RAD) markers
Authors: Macher Jan‐Niklas , Rozenberg Andrey , Pauls Steffen U. , Tollrian Ralph , Wagner Rüdiger , Leese Florian 
Published: January 2015

AbstractRepeated Quaternary glaciations have significantly shaped the present distribution and diversity of several European species in aquatic and terrestrial habitats. To study the phylogeography of freshwater invertebrates, patterns of intraspecific variation have been examined primarily using mitochondrial DNA markers that may yield results unrepresentative of the true species history. Here, population genetic parameters were inferred for a montane aquatic caddisfly, Thremma gallicum, by sequencing a 658‐bp fragment of the mitochondrial CO1 gene, and 12,514 nuclear RAD loci. T. gallicum has a highly disjunct distribution in southern and central Europe, with known populations in the Cantabrian Mountains, Pyrenees, Massif Central, and Black Forest. Both datasets represented rangewide sampling of T. gallicum. For the CO1 dataset, this included 352 specimens from 26 populations, and for the RAD dataset, 17 specimens from eight populations. We tested 20 competing phylogeographic scenarios using approximate Bayesian computation (ABC) and estimated genetic diversity patterns. Support for phylogeographic scenarios and diversity estimates differed between datasets with the RAD data favouring a southern origin of extant populations and indicating the Cantabrian Mountains and Massif Central populations to represent highly diverse populations as compared with the Pyrenees and Black Forest populations. The CO1 data supported a vicariance scenario (north–south) and yielded inconsistent diversity estimates. Permutation tests suggest that a few hundred polymorphic RAD SNPs are necessary for reliable parameter estimates. Our results highlight the potential of RAD and ABC‐based hypothesis testing to complement phylogeographic studies on non‐model species.
Metabolic variation in natural populations of wild yeast
Authors: Samani Pedram , Low‐Decarie Etienne , McKelvey Kyra , Bell Thomas , Burt Austin , Koufopanou Vassiliki , Landry Christian R. , Bell Graham 
Published: January 2015

AbstractEcological diversification depends on the extent of genetic variation and on the pattern of covariation with respect to ecological opportunities. We investigated the pattern of utilization of carbon substrates in wild populations of budding yeast Saccharomyces paradoxus. All isolates grew well on a core diet of about 10 substrates, and most were also able to grow on a much larger ancillary diet comprising most of the 190 substrates we tested. There was substantial genetic variation within each population for some substrates. We found geographical variation of substrate use at continental, regional, and local scales. Isolates from Europe and North America could be distinguished on the basis of the pattern of yield across substrates. Two geographical races at the North American sites also differed in the pattern of substrate utilization. Substrate utilization patterns were also geographically correlated at local spatial scales. Pairwise genetic correlations between substrates were predominantly positive, reflecting overall variation in metabolic performance, but there was a consistent negative correlation between categories of substrates in two cases: between the core diet and the ancillary diet, and between pentose and hexose sugars. Such negative correlations in the utilization of substrate from different categories may indicate either intrinsic physiological trade‐offs for the uptake and utilization of substrates from different categories, or the accumulation of conditionally neutral mutations. Divergence in substrate use accompanies genetic divergence at all spatial scales in S. paradoxus and may contribute to race formation and speciation.
Hierarchical analysis of genetic structure in the habitat‐specialist Eastern Sand Darter (Ammocrypta pellucida)
Authors: Ginson Robert , Walter Ryan P. , Mandrak Nicholas E. , Beneteau Courtney L. , Heath Daniel D. 
Published: January 2015

AbstractQuantifying spatial genetic structure can reveal the relative influences of contemporary and historic factors underlying localized and regional patterns of genetic diversity and gene flow – important considerations for the development of effective conservation efforts. Using 10 polymorphic microsatellite loci, we characterize genetic variation among populations across the range of the Eastern Sand Darter (Ammocrypta pellucida), a small riverine percid that is highly dependent on sandy substrate microhabitats. We tested for fine scale, regional, and historic patterns of genetic structure. As expected, significant differentiation was detected among rivers within drainages and among drainages. At finer scales, an unexpected lack of within‐river genetic structure among fragmented sandy microhabitats suggests that stratified dispersal resulting from unstable sand bar habitat degradation (natural and anthropogenic) may preclude substantial genetic differentiation within rivers. Among‐drainage genetic structure indicates that postglacial (14 kya) drainage connectivity continues to influence contemporary genetic structure among Eastern Sand Darter populations in southern Ontario. These results provide an unexpected contrast to other benthic riverine fish in the Great Lakes drainage and suggest that habitat‐specific fishes, such as the Eastern Sand Darter, can evolve dispersal strategies that overcome fragmented and temporally unstable habitats.
5′‐Ectonucleotidase/CD73 expression on lymph‐circulating lymphocytes and lymphatic endothelial cells offers new paths to explore barrier function
Authors: Sidibé Adama , Imhof Beat A 
Published: January 2015

5′‐Nucleotidase/CD73 is a key enzyme in the regulation of purinergic signaling, hydrolyzing extracellular AMP to produce adenosine, which is critical in the blood vascular system and in immunosuppression. CD73 is expressed by both blood endothelial cells and lymphatic endothelial cells. Although the role of CD73 on blood endothelial cells in controlling vascular permeability and leukocyte trafficking has been studied, the role of lymphatic CD73 has thus far remained unknown. In this issue of European Journal of Immunology, Yegutkin et al. [Eur. J. Immunol. 2015. 45: 562–573] compare CD73 activity in the endothelia of lymphatics and blood vessels and investigate the CD73+ lymphocyte subpopulations possibly involved in immunoregulation. This Commentary will discuss how the authors′ work sheds light on the differential use of CD73 by these two cell populations to control endothelial permeability and sprouting.
Rapid determination of branched chain amino acids in human blood plasma by pressure‐assisted capillary electrophoresis with contactless conductivity detection
Authors: Tůma Petr , Gojda Jan 
Published: January 2015

A CE method with contactless conductivity detection has been developed for the clinical determination of the branched chain amino acids (BCAAs) valine, isoleucine and leucine in human blood plasma. The CE separation was performed in an optimised BGE with composition of 3.2 M acetic acid in 20% v/v methanol, pH 2.0. The achieved separation time was 125 s when using a capillary with an effective length of 14.7 cm, electric field intensity of 0.96 kV/cm and simultaneous application of a hydrodynamic pressure of 50 mbar. The separation efficiency in blood plasma equalled 461 000 theoretical plates/m for valine and isoleucine, and 455 000 theoretical plates/m for leucine; the detection limits are equal to 0.4 μM for all three amino acids. The RSD values for repeatability of the migration time equalled 0.1% for measurements during a single day and 0.3% for measurements on different days; the RSD values for repeatability of the peak areas equalled 2.3–2.6% for measurements during a single day and 2.7–4.6% for measurements on different days. It followed from the performed tests that the plasmatic levels of BCAAs attain a maximum 60 min after intravenous application of an infusion of BCAAs.
Laser‐induced shockwave paired with FRET: A method to study cell signaling
Authors: Gomez‐Godinez Veronica , Preece Daryl , Shi Linda , Khatibzadeh Nima , Rosales Derrick , Pan Yijia , Lei Lie , Wang Yingxiao , Berns Michael W. 
Published: January 2015

ABSTRACTCells within the body are subject to various forces; however, the details concerning the way in which cells respond to mechanical stimuli are not well understood. We demonstrate that laser‐induced shockwaves (LIS) combined with biosensors based on fluorescence resonance energy transfer (FRET) is a promising new approach to study biological processes in single live cells. As “proof‐of‐concept,” using a FRET biosensor, we show that in response to LIS, cells release intracellular calcium. With the parameters used, cells retain their morphology and remain viable. LIS combined with FRET permits observation of the cells immediate response to a sudden shear force. Microsc. Res. Tech. 78:195–199, 2015. © 2015 Wiley Periodicals, Inc.