bluuebunny/crossref_metadata_2025_split huggingface dataset:
Catalytic Enantioselective Inverse Electron Demand Hetero‐Diels–Alder Reaction with Allylsilanes
Authors: Matsumura Yuki , Suzuki Takahiro , Sakakura Akira , Ishihara Kazuaki 
Published: April 2014

AbstractThe first diastereo‐ and enantioselective inverse electron demand hetero‐Diels–Alder reaction of β,γ‐unsaturated α‐ketoesters with allylsilanes is described. Chiral copper(II) catalysts successfully activate the β,γ‐unsaturated α‐ketoesters and promote the reaction with allylsilanes with excellent enantioselectivities. This process represents a new entry to chiral oxanes.
Accessing the Single‐Electron Manifold: Magnesium‐mediated Hydrogen Release from Silanes
Authors: Liptrot David J. , Hill Professor Michael S. , Mahon Mary F. 
Published: April 2014

AbstractReactions of TEMPO (2,2,6,6‐tetramethyl‐1‐piperidinyloxy) with magnesium hydride species initiate oxidative hydrogen release, which may be elaborated to a catalytic regime within a manifold constructed about sequential TEMPO‐mediated redox and MgO/SiH metathesis processes.
Long‐Term Safety of Subcutaneous Abatacept in Rheumatoid Arthritis: Integrated Analysis of Clinical Trial Data Representing More Than Four Years of Treatment
Authors: Alten Rieke , Kaine Jeffrey , Keystone Edward , Nash Peter , Delaet Ingrid , Genovese Mark C. 
Published: April 2014

ObjectiveTo investigate the safety of long‐term subcutaneous (SC) abatacept treatment using integrated clinical trial data obtained in patients with rheumatoid arthritis refractory to traditional disease‐modifying antirheumatic drugs.MethodsData from the double‐blind and open‐label phases of 5 clinical trials of SC abatacept were pooled. The overall and 6‐month incidence rates were calculated as events per 100 patient‐years of exposure.ResultsThis analysis included 1,879 patients with 4,214.6 patient‐years of exposure to SC abatacept. The mean ± SD length of exposure was 27.3 ± 9.1 months. The reported incidence rate of serious infections was 1.79 (95% confidence interval [95% CI] 1.42–2.24); the most frequent infections were pneumonia (incidence rate 0.36 [95% CI 0.22–0.59]), urinary tract infection (incidence rate 0.14 [95% CI 0.06–0.32]), and gastroenteritis (incidence rate 0.10 [95% CI 0.04–0.25]). Tuberculosis occurred rarely (incidence rate 0.09 [95% CI 0.04–0.25]). The reported incidence rate of malignancies was 1.32 (95% CI 1.01–1.72), and the most common was solid organ malignancy (incidence rate 0.69 [95% CI 0.48–0.99]). The incidence rate of autoimmune events was 1.37 (95% CI 1.06–1.78), and the most frequent events were psoriasis (incidence rate 0.33 [95% CI 0.20–0.56]) and Sjögren's syndrome (incidence rate 0.24 [95% CI 0.13–0.44]). The reported incidence rate of local injection site reactions was 1.72 (95% CI 1.36–2.17); these events occurred primarily during the first 6 months of treatment, and almost all were of mild or moderate intensity. The incidence rates of serious infections, malignancies, autoimmune events, and injection site reactions did not increase over time.ConclusionLong‐term treatment with SC abatacept was associated with low incidence rates of serious infections, malignancies, and autoimmune events and was well tolerated, with infrequent injection site reactions. These findings are consistent with those related to treatment with intravenous abatacept. Long‐term treatment with SC abatacept did not lead to new safety signals over time.
Development and Validation of the HScore, a Score for the Diagnosis of Reactive Hemophagocytic Syndrome
Authors: Fardet Laurence , Galicier Lionel , Lambotte Olivier , Marzac Christophe , Aumont Cedric , Chahwan Doumit , Coppo Paul , Hejblum Gilles 
Published: April 2014

ObjectiveBecause it has no unique clinical, biologic, or histologic features, reactive hemophagocytic syndrome may be difficult to distinguish from other diseases such as severe sepsis or hematologic malignancies. This study was undertaken to develop and validate a diagnostic score for reactive hemophagocytic syndrome.MethodsA multicenter retrospective cohort of 312 patients who were judged by experts to have reactive hemophagocytic syndrome (n = 162), were judged by experts to not have reactive hemophagocytic syndrome (n = 104), or in whom the diagnosis of reactive hemophagocytic syndrome was undetermined (n = 46) was used to construct and validate the reactive hemophagocytic syndrome diagnostic score, called the HScore. Ten explanatory variables were evaluated for their association with the diagnosis of hemophagocytic syndrome, and logistic regression was used to calculate the weight of each criterion included in the score. Performance of the score was assessed using developmental and validation data sets.ResultsNine variables (3 clinical [i.e., known underlying immunosuppression, high temperature, organomegaly], 5 biologic [i.e., triglyceride, ferritin, serum glutamic oxaloacetic transaminase, and fibrinogen levels, cytopenia], and 1 cytologic [i.e., hemophagocytosis features on bone marrow aspirate]) were retained in the HScore. The possible number of points assigned to each variable ranged from 0–18 for known underlying immunosuppression to 0–64 for triglyceride level. The median HScore was 230 (interquartile range [IQR] 203–257) for patients with a positive diagnosis of reactive hemophagocytic syndrome and 125 (IQR 91–150) for patients with a negative diagnosis. The probability of having hemophagocytic syndrome ranged from <1% with an HScore of ≤90 to >99% with an HScore of ≥250.ConclusionThe HScore can be used to estimate an individual's risk of having reactive hemophagocytic syndrome. This scoring system is freely available online (http://saintantoine.aphp.fr/score/).
Synthetic and Computational Evaluation of Regiodivergent Epoxide Opening for Diol and Polyol Synthesis
Authors: Gansäuer Andreas , Karbaum Peter , Schmauch David , Einig Martin , Shi Lili , Anoop Anakuthil , Neese Frank 
Published: April 2014

AbstractIn a combined synthetic and computational study, the factors governing the selectivity of the titanocene(III)‐catalyzed regiodivergent epoxide opening (REO) with Kagan’s complex via electron transfer leading to derivatives of 1,2‐, 1,3‐, and 1,4‐diols were investigated. In this manner, valuable building blocks for the synthesis of 1,3‐ and 1,4‐diols were identified. The computational study provides crucial structural features and energies of the transition states of ring opening that are important for the design of more selective catalysts.
Effects of methyl jasmonate and salicylic acid on tanshinone production and biosynthetic gene expression in transgenic Salvia miltiorrhiza hairy roots
Authors: Hao Xiaolong , Shi Min , Cui Lijie , Xu Chao , Zhang Yanjie , Kai Guoyin 
Published: April 2014

AbstractTanshinone is a group of active diterpenes, which are widely used in the treatment of cardiovascular disease. In this study, methyl jasmonate (MJ) and salicylic acid (SA) were used to investigate their effects on tanshinone accumulation and biosynthetic gene expression in the hairy roots of geranylgeranyl diphosphate synthase (SmGGPPS) overexpression line (G50) in Salvia miltiorrhiza. High‐performance liquid chromatography analysis showed that total tanshinone content in G50 was obviously increased by 3.10‐fold (11.33 mg/g) with MJ at 36 H and 1.63 times (5.95 mg/g) after SA treatment for 36 H in comparison with their mimic treatment control. Furthermore, quantitative reverse‐transcription PCR analysis showed that the expression of isopentenyl‐diphosphate delta‐isomerase (SmIPPI), SmGGPPS, copalyl diphosphate synthase (SmCPS), and kaurene synthase‐like (SmKSL) increased significantly with MJ treatment. However, the expression of SmIPPI reached the highest level at 144 H, whereas those of SmGGPPS, SmCPS, and SmKSL only increased slightly with SA treatment. The two elicitor treatments suggested that tanshinone accumulation positively correlated to the expression of key genes such as SmGGPPS, SmCPS, and SmKSL. Meanwhile, the study also indicated that it was a feasible strategy to combine elicitor treatment with transgenic technology for the enhancement of tanshinone, which paved the way for further metabolic engineering of tanshinone biosynthesis.
Corticosteroid use and risk of orofacial clefts
Authors: Skuladottir Hildur , Wilcox Allen J. , Ma Chen , Lammer Edward J. , Rasmussen Sonja A. , Werler Martha M. , Shaw Gary M. , Carmichael Suzan L. 
Published: April 2014

BackgroundMaternal use of corticosteroids during early pregnancy has been inconsistently associated with orofacial clefts in the offspring. A previous report from the National Birth Defect Prevention Study (NBDPS), using data from 1997 to 2002, found an association with cleft lip and palate (odds ratio, 1.7; 95% confidence interval [CI], 1.1–2.6), but not cleft palate only (odds ratio, 0.5, 95%CI, 0.2–1.3). From 2003 to 2009, the study population more than doubled in size, and our objective was to assess this association in the more recent data.MethodsThe NBDPS is an ongoing multi‐state population‐based case‐control study of birth defects, with ascertainment of cases and controls born since 1997. We assessed the association of corticosteroids and orofacial clefts using data from 2372 cleft cases and 5922 controls born from 2003 to 2009. Maternal corticosteroid exposure was based on telephone interviews.ResultsThe overall association of corticosteroids and cleft lip and palate in the new data was 1.0 (95% CI, 0.7–1.4). There was little evidence of associations between specific corticosteroid components or timing and clefts.ConclusionIn contrast to the 1997 to 2002 data from the NBDPS, the 2003 to 2009 data show no association between maternal corticosteroid use and cleft lip and palate in the offspring. Birth Defects Research (Part A) 100:499–506, 2014. © 2014 The Authors Birth Defects Research Part A: Clinical and Molecular Teratology Published by Wiley Periodicals, Inc.
Perioperative management of patients on new oral anticoagulants
Authors: Lai A , Davidson N , Galloway S W , Thachil J 
Published: April 2014

Abstract

Background
New oral anticoagulants (NOACs) offer an alternative to warfarin for preventing stroke in patients with atrial fibrillation. NOACs are expected to replace warfarin and other vitamin K antagonists for most of their indications in the future. Knowledge of the use of NOACs in the perioperative period is important for optimal care.

Methods
Studies that reported on the use of NOACs were identified, focusing on evidence-based guidance relating to the perioperative period. PubMed was searched for relevant articles published between January 2000 and January 2014.

Results
The anticipated expanded clinical use of NOACs such as rivaroxaban (Xarelto™), apixaban (Eliquis™) and dabigatran (Pradaxa™) has the potential to simplify perioperative anticoagulant management because of fewer drug–drug interactions, rapid onset of action, predictable pharmacokinetics and relatively short half-lives. However, coagulation status cannot be monitored by international normalized ratio and no antidotes are currently available. In elective surgery, it is important to discontinue the use of NOACs, with special consideration of renal function as route of elimination. Guidelines for the management of bleeding complications in patients on NOACs are provided, and may be considered for trauma and emergency surgery. Haemodialysis could be considered for bleeding with use of dabigatran. Better options for reversal of the effects of NOACs when bleeding occurs may follow with novel drugs.

Conclusion
Management of NOACs in elective and emergency conditions requires knowledge of time of last intake of drug, current renal function and the planned procedure in order to assess the overall risk of bleeding. Currently no antidote exists to reverse the effects of these drugs.
Li3PO4‐Coated LiNi0.5Mn1.5O4: A Stable High‐Voltage Cathode Material for Lithium‐Ion Batteries
Authors: Chong Jin , Xun Shidi , Zhang Jingping , Song Xiangyun , Xie Haiming , Battaglia Vincent , Wang Rongshun 
Published: April 2014

AbstractLiNi0.5Mn1.5O4 is regarded as a promising cathode material to increase the energy density of lithium‐ion batteries due to the high discharge voltage (ca. 4.7 V). However, the interface between the LiNi0.5Mn1.5O4 cathode and the electrolyte is a great concern because of the decomposition of the electrolyte on the cathode surface at high operational potentials. To build a stable and functional protecting layer of Li3PO4 on LiNi0.5Mn1.5O4 to avoid direct contact between the active materials and the electrolyte is the emphasis of this study. Li3PO4‐coated LiNi0.5Mn1.5O4 is prepared by a solid‐state reaction and noncoated LiNi0.5Mn1.5O4 is prepared by the same method as a control. The materials are fully characterized by XRD, FT‐IR, and high‐resolution TEM. TEM shows that the Li3PO4 layer (<6 nm) is successfully coated on the LiNi0.5Mn1.5O4 primary particles. XRD and FT‐IR reveal that the synthesized Li3PO4‐coated LiNi0.5Mn1.5O4 has a cubic spinel structure with a space group of Fd$\bar 3$m, whereas noncoated LiNi0.5Mn1.5O4 shows a cubic spinel structure with a space group of P4332. The electrochemical performance of the prepared materials is characterized in half and full cells. Li3PO4‐coated LiNi0.5Mn1.5O4 shows dramatically enhanced cycling performance compared with noncoated LiNi0.5Mn1.5O4.
Alkyl Ammonium Cation Stabilized Biocidal Polyiodides with Adaptable High Density and Low Pressure
Authors: He Chunlin , Parrish Damon A. , Shreeve Jean'ne M. 
Published: April 2014

AbstractThe effective application of biocidal species requires building the active moiety into a molecular back bone that can be delivered and decomposed on demand under conditions of low pressure and prolonged high‐temperature detonation. The goal is to destroy storage facilities and their contents while utilizing the biocidal products arising from the released energy to destroy any remaining harmful airborne agents. Decomposition of carefully selected iodine‐rich compounds can produce large amounts of the very active biocides, hydroiodic acid (HI) and iodine (I2). Polyiodide anions, namely, I3−, I5−, which are excellent sources of such biocides, can be stabilized through interactions with large, symmetric cations, such as alkyl ammonium salts. We have designed and synthesized suitable compounds of adaptable high density up to 3.33 g cm−3 that are low‐pressure polyiodides with various alkyl ammonium cations, deliverable iodine contents of which range between 58.0–90.9 %.
Water Repellency in Hydrophobic Nanocapsules—Molecular View on Dewetting
Authors: Müller Achim , Garai Somenath , Schäffer Christian , Merca Alice , Bögge Hartmut , Al‐Karawi Ahmed Jasim M. , Prasad Thazhe Kootteri 
Published: April 2014

AbstractThe hydrophobic effect plays a major role in a variety of important phenomena in chemistry, materials science and biology, for instance in protein folding and protein–ligand interactions. Studies—performed within cavities of the unique metal oxide based porous capsules of the type {(pentagon)12(linker)30}≡{(W)W5}12{Mo2(ligand)}30 with different acetate/water ligand ratios—have provided unprecedented results revealing segregation/repellency of the encapsulated “water” from the internal hydrophobic ligand walls of the capsules, while the disordered water molecules, interacting strongly with each other via hydrogen bonding, form in all investigated cases the same type of spherical shell. The present results can be (formally) compared—but only regarding the repellency effect—with the amazing “action” of the (super)hydrophobic Lotus (Nelumbo) leaves, which are self‐cleaning based on water repellency resulting in the formation of water droplets picking up dirt. The present results were obtained by constructing deliberately suitable hydrophobic interiors within the mentioned capsules.
A New 3,5‐Bisporphyrinylpyridine Derivative as a Fluorescent Ratiometric Probe for Zinc Ions
Authors: Moura Nuno M. M. , Núñez Cristina , Santos Sérgio M. , Faustino M. Amparo F. , Cavaleiro José A. S. , Almeida Paz Filipe A. , Neves M. Graça P. M. S. , Capelo José Luis , Lodeiro Carlos 
Published: April 2014

AbstractA new 3,5‐disubstituted pyridine with two porphyrin moieties was prepared through an efficient synthetic approach involving 2‐formyl‐5,10,15,20‐tetraphenylporphyrin (1), piperidine, and catalytic amounts of [La(OTf)3]. 3,5‐Bis(5,10,15,20‐tetraphenylporphyrin‐2‐ylmethyl)pyridine (2) was fully characterized and its sensing ability towards Zn2+, Cu2+, Hg2+, Cd2+, and Ag+ was evaluated in solution by absorption and fluorescence spectroscopy and in gas phase by using matrix‐assisted laser desorption/ionization (MALDI)‐TOF mass spectrometry. Strong changes in the ground and excited state were detected in the case of the soft metal ions Zn2+, Cd2+, Hg2+, and Cu2+. A three‐metal‐per‐ligand molar ratio was obtained in all cases and a significant ratiometric behavior was observed in the presence of Zn2+ with the appearance of a new band at 608 nm, which can be assigned to a metal‐to‐ligand charge transfer. The system was able to quantify 79 ppb of Zn2+ and the theoretical calculations are in accordance with the stoichiometry observed in solution. The gas‐phase sensorial ability of compound 2 towards all metal ions was confirmed by using MALDI‐TOF MS and in solid state by using polymeric films of polymethylmethacrylate (PMMA) doped with ligand 2. The results showed that compound 2 can be analytically used to develop new colorimetric molecular devices that are able to discriminate between Hg2+ and Zn2+ in solid phase. The crystal structure of ZnII complex of 3,5‐bisporphyrinylpyridine was unequivocally elucidated by using single‐crystal X‐ray diffraction studies.
Stereocontrol in Dinuclear Triple Lithium‐Bridged Titanium(IV) Complexes: Solving Some Stereochemical Mysteries
Authors: Albrecht Markus , Isaak Elisabeth , Moha Verena , Raabe Gerhard , Fröhlich Roland 
Published: April 2014

AbstractCompounds 1 a–f‐H2 form “monomeric” triscatecholate titanium(IV) complexes [Ti(1 a–f)3]2−, which in the presence of Li cations are in equilibrium with the triple lithium‐bridged “dimers” [Li3(Ti(1 a–f)3)2]−. The equilibrium strongly depends on the donor ability of the solvent. Usually, in solvents with high donor ability, the stereochemically labile monomer is preferred, whereas in nondonor solvents, the dimer is the major species. In the latter, the stereochemistry at the complex units is “locked”. The configuration at the titanium(IV) triscatecholates is influenced by addition of chiral ammonium countercations. In this case, the induced stereochemical information at the monomer is transferred to the dimer. Alternatively, the configuration at the metal complexes can be controlled by enantiomerically pure ester side chains. Due to the different orientation of the ester groups in the monomer or dimer, opposite configurations of the triscatecholates were observed by circular dichroism (CD) spectroscopy for [Ti(1 c–e)3]2− or [Li3(Ti(1 c–e)3)2]−. A surprising exception was found for the dimer [Li3(Ti(1 f)3)2]−. Herein, the dimer is the dominating species in weak donor (methanol), as well as strong donor (DMSO), solvents. This is due to the bulkiness of the ester substituent destabilizing the monomer. Due to the size of the substituent in [Li3(Ti(1 f)3)2]− the esters have to adopt an unusual conformation in the dimer resulting in a stereocontrol of the small methyl group. Following this, opposite stereocontrol mechanisms were observed for the central metal‐complex units of [Li3(Ti(1 c–e)3)2]− or [Li3(Ti(1 f)3)2]−.
Water Repellency in Hydrophobic Nanocapsules—Molecular View on Dewetting
Authors: Müller Achim , Garai Somenath , Schäffer Christian , Merca Alice , Bögge Hartmut , Al‐Karawi Ahmed Jasim M. , Prasad Thazhe Kootteri 
Published: April 2014

AbstractInvited for the cover of this issue is the group of Achim Müller at the University of Bielefeld. The image (including artwork from Hartmut Bögge) depicts manifestations of the ubiquitous hydrophobic effects which play a crucial role in general biology, for example, the so‐called “self‐cleaning properties” of the Lotus leaves (model shown), in structural biology and for many practical applications in daily life. The new results refer to synthetic hydrophobic nanocapsules in which encapsulated water is repelled from the inner wall (left), in sharp contrast to the situation found in related hydrophilic capsules (right). Read the full text of the article at 10.1002/chem.201402216.
Electro‐Fenton Degradation of Methylene Blue Using Polyacrylonitrile‐Based Carbon Fiber Brush Cathode
Authors: Xia Guangsen , Lu Yonghong , Gao Xueli , Gao Congjie , Xu Haibo 
Published: April 2014

AbstractA polyacrylonitrile‐based carbon fiber brush (PAN‐CFB) cathode was firstly used to decolorize and degrade methylene blue (MB) in Na2SO4 solution via electro‐Fenton reaction between H2O2 from oxygen reduction and ferrous ions (Fe2+) externally added. The optimal current value for H2O2 production was 300 mA, with a maximum H2O2 concentration of 185 mg L−1 and current efficiency of 68% after 60 min, indicating that PAN‐based CF is a promising electrode material for 2 e− oxygen reduction reaction. Additionally, the effect of different parameters, such as the initial pH of the dye solution, Fe2+ and initial dye concentration on the decolorization efficiency, and COD removal was thoroughly investigated in simulated wastewater containing MB. The results showed that the electro‐Fenton system using the PAN‐CFB cathode had a wide applicable pH range 3.00–7.00, and the optimal Fe2+ concentration was 0.3 mmol L−1. Moreover, under the conditions of 300 mA current, pH 3.00, and 0.3 mmol L−1 Fe2+, a nearly 100% color removal after 30 min, 95.9% chemical oxygen demand (COD) removal and the low electrochemical energy consumption of 11.6 kWh kg−1 COD after 60 min for 100 mg L−1 MB solution were obtained.
Systems with Competing Interlayer Interactions and Modulations in One Direction: Finding their Structures
Authors: Čepič Mojca 
Published: April 2014

AbstractComplex structures in polar smectic systems can be studied within framework of discrete phenomenological models. Considered interactions are usually described by nonlinear trigonometric functions that do not allow for a straightforward search for solutions. The review of three methods reported in the literature are presented and their appropriateness, advantages and disadvantages are discussed. Examples are given as an illustration for each method.
Far‐Red Organic Fluorophores Contain a Fluorescent Impurity
Authors: Stone Matthew B. , Veatch Sarah L. 
Published: April 2014

AbstractFar‐red organic fluorophores commonly used in traditional and super‐resolution localization microscopy are found to contain a fluorescent impurity with green excitation and near‐red emission. This near‐red fluorescent impurity can interfere with some multicolor stochastic optical reconstruction microscopy/photoactivated localization microscopy measurements in live cells and produce subtle artifacts in chemically fixed cells. We additionally describe alternatives to avoid artifacts in super‐resolution localization microscopy.
Ethanol Oxidation on Pt Single‐Crystal Electrodes: Surface‐Structure Effects in Alkaline Medium
Authors: Busó‐Rogero Carlos , Herrero Enrique , Feliu Juan M. 
Published: April 2014

AbstractEthanol oxidation in 0.1 M NaOH on single‐crystal electrodes has been studied using electrochemical and FTIR techniques. The results show that the activity order is the opposite of that found in acidic solutions. The Pt(111) electrode displays the highest currents and also the highest onset potential of all the electrodes. The onset potential for the oxidation of ethanol is linked to the adsorption of OH on the electrode surface. However, small (or even negligible) amounts of COads and carbonate are detected by FTIR, which implies that cleavage of the CC bond is not favored in this medium. The activity of the electrodes diminishes quickly upon cycling. The diminution of the activity is proportional to the measured currents and is linked to the formation and polymerization of acetaldehyde, which adsorbs onto the electrode surface and prevents further oxidation.