bluuebunny/crossref_metadata_2025_split huggingface dataset:
A 3D Nanoporous Ni–Mo Electrocatalyst with Negligible Overpotential for Alkaline Hydrogen Evolution
Authors: Wang Yuhang , Zhang Guoxin , Xu Wenwen , Wan Pengbo , Lu Zhiyi , Li Yaping , Sun Xiaoming 
Published: June 2014

Abstract3D Ni–Mo electrocatalysts with well‐controlled composition, dimensions and nanoporosity are fabricated using a facile and effective electrodeposition technique on Cu foam. These catalysts exhibit enhanced stability and activity for the hydrogen evolution reaction (HER). By optimizing the Ni/Mo ratio, electrodeposition current density, and reaction time, the overpotential for the HER is reduced to 10 mV. The ultrahigh activity and stability of these catalysts are the highest among non‐precious‐metal electrocatalysts previously reported. The optimized Ni–Mo electrocatalyst has similar overpotential and a much higher current density compared to Pt/C. The improved HER performance is attributed to the Ni/Mo ratio (4:1), the large surface area, and the in situ growth method, which provides a well‐defined catalyst. These catalysts are potentially an attractive alternative to Pt in HERs, and therefore represent new technological opportunities for the development of renewable and economic hydrogen production.
Oleochemical‐Tethered SBA‐15‐Type Silicates with Tunable Nanoscopic Order, Carboxylic Surface, and Hydrophobic Framework: Cellular Toxicity, Hemolysis, and Antibacterial Activity
Authors: Pędziwiatr‐Werbicka Elżbieta , Miłowska Katarzyna , Podlas Marta , Marcinkowska Monika , Ferenc Małgorzata , Brahmi Younes , Katir Nadia , Majoral Jean‐Pierre , Felczak Aleksandra , Boruszewska Aleksandra , Lisowska Katarzyna , Bryszewska Maria , El Kadib Abdelkrim 
Published: June 2014

AbstractNovel silicates were prepared by using silylated natural fatty acids (derived from triglyceride renewable oils) as co‐condensing reagents in presence of tetraethyl orthosilicate (TEOS) and the triblock copolymer, pluronic P123, as a structure directing agent. A series of carboxylic acid functionalized SBA‐15‐type mesoporous silicates were obtained with tunable nanoscopic order and reactive functional groups that allow the conjugation of amino probes by peptide coupling. Photophysical studies of the covalently linked aminopyrene substantiated that the internal framework of these materials have pronounced hydrophobicity. Moreover, phase separation that can emanate from the bulkiness of the starting fatty silanes has been ruled out owing to the absence of excimers after aminopyrene grafting. The hemotoxicity, cytotoxicity, and antimicrobial activity of these novel silicates were then evaluated. Without discrimination, the functionalized silicates show a significant decrease of red blood cell hemolysis as compared to bare SBA‐15‐silica material. Within the modified silicate series, germanium‐free mesoporous silicates induce only a slight decrease in cell viability and, more interestingly, they exhibit negligible hemolytic effect. Moreover, increasing their concentration in the medium reduces the concentration of released hemoglobin as a result of Hb adsorption. Promising antimicrobial properties were also observed for these silicates with a slight dependency on whether phenylgermanium fragments were present within the silicate framework.
High‐Yield Formation of Substituted Tetracyanobutadienes from Reaction of Ynamides with Tetracyanoethylene
Authors: Betou Marie , Kerisit Nicolas , Meledje Esme , Leroux Yann R. , Katan Claudine , Halet Jean‐François , Guillemin Jean‐Claude , Trolez Yann 
Published: June 2014

AbstractA high‐yielding sequence of [2+2] cycloaddition–retroelectrocyclization of ynamides with tetracyanoethylene (TCNE) is described. The reaction provided tetracyanobutadiene (TCBD) species, which were characterized by various techniques. DFT and TD‐DFT calculations were also performed to complement experimental findings.
Enhanced Photoinduced Electron Transfer at the Surface of Charged Lipid Bilayers
Authors: Limburg Bart , Laisné Guillaume , Bouwman Elisabeth , Bonnet Sylvestre 
Published: June 2014

AbstractPhotocatalytic systems often suffer from poor quantum yields due to fast charge recombination: The energy‐wasting annihilation of the photochemically created charge‐separated state. In this report, we show that the efficiency of photoinduced electron transfer from a sacrificial electron donor to positively charged methyl viologen, or to negatively charged 5,5′‐dithiobis(2‐nitrobenzoate), increases dramatically upon addition of charged phospholipid vesicles if the charge of the lipids is of the same sign as that of the electron acceptor. Centrifugation and UV/Vis titration experiments showed that the charged photosensitizers adsorb at the liposome surface, that is, where the photocatalytic reaction takes place. The increased photoelectron transfer efficiency in the presence of charged liposomes has been ascribed to preferential electrostatic interactions between the photosensitizer and the membrane, which prevents the formation of photosensitizer–electron‐acceptor complexes that are inactive towards photoreduction. Furthermore, it is shown that the addition of liposomes results in a decrease in photoproduct inhibition, which is caused by repulsion of the reduced electron acceptor by the photocatalytic site. Thus, liposomes can be used as a support to perform efficient photocatalysis; the charged photoproducts are pushed away from the liposomes and represent “soluble electrons” that can be physically separated from the place where they were generated.
Synthesis of Unsymmetrically Substituted Phosphane Oxides (R1R2P(O)H) and Phosphinous Acids (R1R2POH)
Authors: Allefeld Nadine , Grasse Michael , Ignat'ev Nikolai , Hoge Berthold 
Published: June 2014

AbstractInvited for the cover of this issue is the group of Berthold Hoge at the University of Bielefeld. The image depicts the delicate balance between the unusual form of a phosphinous acid with respect to the corresponding phosphane oxide tautomer by the influence of electron‐withdrawing groups. Read the full text of the article at 10.1002/chem.201402425.
Development of an Iron(II)‐Catalyzed Aerobic Catechol Cleavage and Biomimetic Synthesis of Betanidin
Authors: Guimond Nicolas , Mayer Peter , Trauner Dirk 
Published: June 2014

AbstractAn aerobic iron(II)‐catalyzed cleavage of catechols was developed. This reaction allows for the preparation of 2‐methoxy‐2 H‐pyrans that can be employed as versatile building blocks for synthesis. The utility of this biomimetic oxidative cleavage is featured in the synthesis of betanidin, a natural colorant with antioxidant properties.
2‐Nitroveratryl as a Photocleavable Thiol‐Protecting Group for Directed Disulfide Bond Formation in the Chemical Synthesis of Insulin
Authors: Karas John A. , Scanlon Denis B. , Forbes Briony E. , Vetter Irina , Lewis Richard J. , Gardiner James , Separovic Frances , Wade John D. , Hossain Mohammed A. 
Published: June 2014

AbstractChemical synthesis of peptides can allow the option of sequential formation of multiple cysteines through exploitation of judiciously chosen regioselective thiol‐protecting groups. We report the use of 2‐nitroveratryl (oNv) as a new orthogonal group that can be cleaved by photolysis under ambient conditions. In combination with complementary S‐pyridinesulfenyl activation, disulfide bonds are formed rapidly in situ. The preparation of Fmoc‐Cys(oNv)‐OH is described together with its use for the solid‐phase synthesis of complex cystine‐rich peptides, such as insulin.
High‐Resolution 3D Proton MRI of Hyperpolarized Gas Enabled by Parahydrogen and Rh/TiO2 Heterogeneous Catalyst
Authors: Kovtunov Kirill V. , Barskiy Danila A. , Coffey Aaron M. , Truong Milton L. , Salnikov Oleg G. , Khudorozhkov Alexander K. , Inozemtseva Elizaveta A. , Prosvirin Igor P. , Bukhtiyarov Valery I. , Waddell Kevin W. , Chekmenev Eduard Y. , Koptyug Igor V. 
Published: June 2014

AbstractSeveral supported metal catalysts were synthesized, characterized, and tested in heterogeneous hydrogenation of propene with parahydrogen to maximize nuclear spin hyperpolarization of propane gas using parahydrogen induced polarization (PHIP). The Rh/TiO2 catalyst with a metal particle size of 1.6 nm was found to be the most active and effective in the pairwise hydrogen addition and robust, demonstrating reproducible results with multiple hydrogenation experiments and stability for ≥1.5 years. 3D 1H magnetic resonance imaging (MRI) of 1 % hyperpolarized flowing gas with microscale spatial resolution (625×625×625 μm3) and large imaging matrix (128×128×32) was demonstrated by using a preclinical 4.7 T scanner and 17.4 s imaging scan time.
[18F]CuCF3: A [18F]Trifluoromethylating Agent for Arylboronic Acids and Aryl Iodides
Authors: Ivashkin Pavel , Lemonnier Gérald , Cousin Jonathan , Grégoire Vincent , Labar Daniel , Jubault Philippe , Pannecoucke Xavier 
Published: June 2014

AbstractPositron emission tomography has emerged as the leading method for medical imaging with fluorine‐18 as the most widely used radioactive isotope. Here we report a semi‐automated method for the preparation of valuable [18F]trifluoromethylcopper, as well as its use for the radiosynthesis of [18F]trifluoromethylarenes and heteroarenes. Mild conditions of [18F]trifluoromethylation make this method particularly useful for the radiosynthesis of pharmacologically relevant [18F]trifluoromethylarenes and heteroarenes.
Investigation of the Impact and Compression Behaviour of Wet Granules
Authors: Müller Peter , Aman Sergej , Tomas Jürgen 
Published: June 2014

AbstractDas Materialverhalten dominant elastisch‐plastischer γ‐Al2O3‐Granulate wurde experimentell mittels dynamischer Prall‐ und quasistatischer Druckversuche bis zum Bruch untersucht. Aus dem Vergleich der ermittelten Verteilungen der Bruchgeschwindigkeit und der spezifischen Bruchenergie lassen sich geschwindigkeitsabhängige Einflüsse bei der Beanspruchung wie viskoses Verhalten ableiten. Der Einfluss der Partikelgröße und der Feuchtebeladung bei Prall‐ und Bruchbeanspruchung werden ebenfalls analysiert.
Gyrase ATPase Domain as an Antitubercular Drug Discovery Platform: Structure‐Based Design and Lead Optimization of Nitrothiazolyl Carboxamide Analogues
Authors: Jeankumar Variam Ullas , Renuka Janupally , Kotagiri Sonali , Saxena Shalini , Kakan Shruti Singh , Sridevi Jonnalagadda Padma , Yellanki Swapna , Kulkarni Pushkar , Yogeeswari Perumal , Sriram Dharmarajan 
Published: June 2014

AbstractIn this study, we explored the pharmaceutically underexploited mycobacterial gyrase ATPase (GyrB) domain as a template for a structure‐based virtual screening of our in‐house (BITS Pilani) compound collection to discover new inhibitors targeting Mycobacterium tuberculosis (M.tb.) The hit identified was further customized by using a combination of molecular docking and medicinal chemistry strategies to obtain an optimized analogue displaying considerable in vitro enzyme efficacy and bactericidal properties against the M.tb. H37Rv strain. The binding affinity of the ligand toward the GyrB domain was reascertained by differential scanning fluorimetry experiments. Further evaluation of the hERG toxicity (a major limitation among the previously reported N‐linked aminopiperidine analogues) indicated these molecules to be completely devoid of cardiotoxicity, a significant achievement within this class.
Genetic and intermediate phenotypic susceptibility markers of gastric cancer in Hispanic Americans: A case‐control study
Authors: Sun Yuhui , Gu Jian , Ajani Jaffer A. , Chang David W. , Wu Xifeng , Stroehlein John R. 
Published: June 2014

BACKGROUNDHispanics are the largest nonwhite ethnic group in the US population, and they have higher incidence and mortality rates for gastric cancer (GC) than whites and Asians. Studies have identified several genetic susceptibility loci and intermediate phenotypic biomarkers for GC in whites and Asians. No studies have evaluated genetic susceptibility and intermediate phenotypic biomarkers in Hispanics.METHODSIn a case‐control study of 132 Hispanic patients with GC (cases) and a control group of 125 Hispanics (controls), the authors evaluated the association of 5 single nucleotide polymorphisms (SNPs) that predispose whites and/or Asians to GC and of 2 intermediate phenotypic markers in peripheral blood leukocytes, ie, telomere length and mitochondrial DNA (mtDNA) copy number, with the GC risk.RESULTSThe variant C allele of the reference SNP rs2294008 in the PSCA gene was associated with a significantly reduced risk of GC (per allele‐adjusted odds ratio [aOR], 0.51; 95% confidence interval [CI], 0.33‐0.77; P = .002). Leukocyte mtDNA copy numbers were significantly lower in GC cases (mean ± standard deviation, 0.91 ± 0.28) than in controls (1.29 ± 0.42; P < .001). When individuals were dichotomized into high and low mtDNA copy number groups based on the median mtDNA copy number value in the controls, those who had a low mtDNA copy number had a significantly increased risk of GC (aOR, 11.00; 95% CI, 4.79‐25.23; P < .001) compared with those who had a high mtDNA copy number. Telomere length was not associated significantly with the risk of GC (aOR, 1.21; 95% CI, 0.65‐2.27; P = .551).CONCLUSIONSHispanics share certain genetic susceptibility loci and intermediate phenotypic GC biomarkers with whites and Asians and may also have distinct genetic susceptibility factors. Cancer 2014;120:3040–3048. © 2014 American Cancer Society.
Suicidal ideation in prostate cancer survivors: Understanding the role of physical and psychological health outcomes
Authors: Recklitis Christopher J. , Zhou Eric S. , Zwemer Eric K. , Hu Jim C. , Kantoff Philip W. 
Published: June 2014

BACKGROUNDEpidemiological studies have shown prostate cancer (PC) survivors are at an increased risk of suicide compared with the general population, but to the authors' knowledge very little is known regarding what factors are associated with this increased risk. The current study examined the prevalence of suicidal ideation (SI) and its association with cancer treatment and posttreatment physical and emotional health in a cohort of long‐term PC survivors.METHODSA total of 693 PC survivors (3‐8 years after diagnosis) completed a mailed survey on physical and psychological functioning, including cancer treatments, the Short Form‐12 (SF‐12), the Expanded Prostate Cancer Index Composite Instrument (EPIC‐26), a depression rating scale, and 8 items regarding recent suicidal thoughts and behaviors.RESULTSA total of 86 PC survivors (12.4%) endorsed SI, with 10 individuals (1.4%) reporting serious SI. Serious SI was more common in this sample compared with age‐adjusted and sex‐adjusted normative data. SI was not associated with most demographic variables, or with PC stage or treatments. However, SI was found to be significantly associated with employment status, poor physical and emotional functioning, greater symptom burden on the EPIC‐26, higher frequency of significant pain, and clinically significant depression (P < .01). In an adjusted logistic model, poor physical and emotional function, including disability status and pain, were found to be associated with SI (P < .05), even after adjusting for depression.CONCLUSIONSA significant percentage of PC survivors report recent SI, which is associated with both physical and psychological dysfunction, but not PC treatments. The results of the current study help to explain the increased risk of suicide previously reported in PC survivors and have important implications for identifying and treating those survivors at greatest risk of suicidality. Cancer 2014;120:3393–3400. © 2014 American Cancer Society.
Impact of Medicare Part D on out‐of‐pocket drug costs and medical use for patients with cancer
Authors: Kircher Sheetal M. , Johansen Michael E. , Nimeiri Halla S. , Richardson Caroline R. , Davis Matthew M. 
Published: June 2014

BACKGROUNDMedicare Part D was designed to reduce out‐of‐pocket (OOP) costs for Medicare beneficiaries, but to the authors' knowledge the extent to which this occurred for patients with cancer has not been measured to date. The objective of the current study was to examine the impact of Medicare Part D eligibility on OOP cost for prescription drugs and use of medical services among patients with cancer.METHODSUsing the Medical Expenditure Panel Survey (MEPS) for the years 2002 through 2010, a differences‐in‐differences analysis estimated the effects of Medicare Part D eligibility on OOP pharmaceutical costs and medical use. The authors compared per capita OOP cost and use between Medicare beneficiaries (aged ≥65 years) with cancer to near‐elderly patients aged 55 years to 64 years with cancer. Statistical weights were used to generate nationally representative estimates.RESULTSA total of 1878 near‐elderly and 4729 individuals with Medicare were included (total of 6607 individuals). The mean OOP pharmaceutical cost for Medicare beneficiaries before the enactment of Part D was $1158 (standard error, ±$52) and decreased to $501 (standard error, ±$30), a decline of 43%. Compared with changes in OOP pharmaceutical costs for nonelderly patients with cancer over the same period, the implementation of Medicare Part D was associated with a further reduction of $356 per person. Medicare Part D appeared to have no significant impact on the use of medications, hospitalizations, or emergency department visits, but was associated with a reduction of 1.55 in outpatient visits.CONCLUSIONSMedicare D has reduced OOP prescription drug costs and outpatient visits for seniors with cancer beyond trends observed for younger patients, with no major impact on the use of other medical services noted. Cancer 2014;120:3378–3384. © 2014 American Cancer Society.
A Physical Pulverization Strategy for Preparing a Highly Active Composite of CoOx and Crushed Graphite for Lithium–Oxygen Batteries
Authors: Ming Jun , Kwak Won‐Jin , Park Jin‐Bum , Shin Chang‐Dae , Lu Jun , Curtiss Larry , Amine Khalil , Sun Yang‐Kook 
Published: June 2014

AbstractA new physical pulverization strategy has been developed to prepare a highly active composite of CoOx and crushed graphite (CG) for the cathode in lithium–oxygen batteries. The effect of CoOx loading on the charge potential in the oxygen evolution reaction (Li2O2→2 Li++O2+2e−) was investigated in coin‐cell tests. The CoOx (38.9 wt %)/CG composite showed a low charge potential of 3.92 V with a delivered capacity of 2 mAh cm−2 under a current density of 0.2 mA cm−2. The charge potential was 4.10 and 4.15 V at a capacity of 5 and 10 mAh cm−2, respectively, with a current density of 0.5 mA cm−2. The stability of the electrolyte and discharge product on the gas‐diffusion layer after the cycling were preliminarily characterized by 1H nuclear magnetic resonance spectroscopy, scanning electron microscopy, X‐ray photoelectron spectroscopy, and X‐ray diffraction. The high activity of the composite was further analyzed by electrochemical impedance spectroscopy, cyclic voltammetry, and potential‐step chronoamperometry. The results indicate that our near‐dry milling method is an effective and green approach to preparing a nanocomposite cathode with high surface area and porosity, while using less solvent. Its relative simplicity compared with the traditional solution method could facilitate its widespread application in catalysis, energy storage, and materials science.
Synthesis and Characterization of a Stable Copper(I) Complex for Radiopharmaceutical Applications
Authors: Bodio Ewen , Boujtita Mohammed , Julienne Karine , Le Saec Patricia , Gouin Sébastien G. , Hamon Jonathan , Renault Eric , Deniaud David 
Published: June 2014

AbstractA highly stable copper(I) complex was obtained starting from a copper(II) salt. This compound was characterized by a combination of several analytical techniques (UV/Vis spectroscopy, energy‐dispersive X‐ray spectroscopy, electrochemistry, and X‐ray photoelectron spectroscopy) and was shown to present an N4Cu structure. These results were confirmed by a density functional calculations study of the binding energy and the electronic structure of model ligand and copper complexes. Preliminary tests of complexation showed a high ability of the corresponding ligand to chelate 64Cu in very diluted medium, which is of interest for developing new positron emission tomography imaging agents. The stability and the kinetic inertness of the complex are promising. In particular, it displayed good redox stability, which is important because in vivo reduction or oxidation of the copper of Cu complexes can lead to demetalation. The rapid microwave‐assisted strategy used to synthesize the ligand was applied to the synthesis of more than ten ligands. One of these was functionalized by an amino group to form a bifunctional chelate for a future bioconjugation for applications in nuclear medicine.
Unveiling TiNb2O7 as an Insertion Anode for Lithium Ion Capacitors with High Energy and Power Density
Authors: Aravindan Vanchiappan , Sundaramurthy Jayaraman , Jain Akshay , Kumar Palaniswamy Suresh , Ling Wong Chui , Ramakrishna Seeram , Srinivasan Madapusi P. , Madhavi Srinivasan 
Published: June 2014

AbstractThis is the first report of the utilization of TiNb2O7 as an insertion‐type anode in a lithium‐ion hybrid electrochemical capacitor (Li‐HEC) along with an activated carbon (AC) counter electrode derived from a coconut shell. A simple and scalable electrospinning technique is adopted to prepare one‐dimensional TiNb2O7 nanofibers that can be characterized by XRD with Rietveld refinement, SEM, and TEM. The lithium insertion properties of such electrospun TiNb2O7 are evaluated in the half‐cell configuration (Li/TiNb2O7) and it is found that the reversible intercalation of lithium (≈3.45 mol) is feasible with good capacity retention characteristics. The Li‐HEC is constructed with an optimized mass loading based on the electrochemical performance of both the TiNb2O7 anode and AC counter electrode in nonaqueous media. The Li‐HEC delivers very high energy and power densities of approximately 43 Wh kg−1 and 3 kW kg−1, respectively. Furthermore, the AC/TiNb2O7 Li‐HEC delivers a good cyclability of 3000 cycles with about 84 % of the initial value.
Comparison of cytotechnologists' and cytopathologists' ASCUS rates preimplementation and postimplementation of the ThinPrep® imaging system
Authors: Selvaggi Suzanne M. 
Published: June 2014

BackgroundThe automated ThinPrep® Imaging System assists the cytotechnologists in the primary screening of ThinPrep® Pap Tests. This study compares the concordance of the cytotechnologists and cytopathologists in the interpretation of Pap Tests as Atypical Squamous Cells of Undetermined Significance (ASCUS) before and after implementation of the Imager in our laboratory.MethodsFrom January 1–December 31, 2011, 12,853 ThinPrep® Pap Tests were processed on a ThinPrep® 3000 Processor, stained by the Papanicolaou method and screened manually by the cytotechnologists. In 2012, 26,581 Pap Tests were processed on a ThinPrep® 3000 Processor, stained with the ThinPrep® Stain, screened on the Image Processor, and reviewed on a Review Scope by the cytotechnologists. All cases interpreted as ASCUS were sent to the cytopathologist for final review.ResultsOverall, 52% of the ASCUS Pap Tests were overcalled by the cytotechnologists on manual screening and 56% were overcalled by the cytotechnologists with use of the ThinPrep® Imaging System, as addressed by the cytopathologist as the final arbitrator.ConclusionIn this study, initial use of a new technology resulted in over interpretation of negative cases as ASCUS. Increased usage and familiarity with the System should lead to pre‐Imager rates. Diagn. Cytopathol. 2015;43:105–107. © 2014 Wiley Periodicals, Inc.