bluuebunny/crossref_metadata_2025_split huggingface dataset:
Aqueous Rechargeable Battery Based on Zinc and a Composite of LiNi1/3Co1/3Mn1/3O2
Authors: Wang Faxing , Liu Yu , Wang Xiaowei , Chang Zheng , Wu Yuping , Holze Rudolf 
Published: April 2015

AbstractA composite of rod‐shaped LiNi1/3Co1/3Mn1/3O2 with graphene nanosheets and multiwall carbon nanotubes (MWCNTs) is assembled by using a hydrothermal method. In the composite, LiNi1/3Co1/3Mn1/3O2 and MWCNTs are wrapped into graphene nanosheets. It exhibits better rate capability in comparison with plain LiNi1/3Co1/3Mn1/3O2 as a positive electrode for an aqueous rechargeable battery, using zinc as the negative electrode. The average charge and discharge voltages of this aqueous rechargeable battery are 1.80 and 1.65 V, respectively. Based on the total weight of the electrode materials of the composite and Zn, its energy density can reach 154 Wh kg−1, which is comparable with that of Ni‐MH batteries. Its cycling behavior is satisfactory.
Facile Synthesis of Hollow Mesoporous CoFe2O4 Nanospheres and Graphene Composites as High‐Performance Anode Materials for Lithium‐Ion Batteries
Authors: Dong Yucheng , Chui Ying‐San , Yang Xia , Ma Ruguang , Lee Jong‐Min , Zapien Juan Antonio 
Published: April 2015

AbstractA novel, facile, self‐assembly approach, based on a gas‐bubble‐template model and assisted by graphene oxide, is developed to fabricate hollow 3D mesoporous CoFe2O4 nanospheres (NSs) and graphene composites. During the hydrothermal process, the oxygen‐containing functional groups and defect sites on the graphene sheets act as nucleation centers to anchor released gas bubbles, providing a soft template for the aggregation of nanosized CoFe2O4 crystallite building blocks to form NSs. Benefiting from the synergistic effect between the hollow 3D mesoporous CoFe2O4 NSs and graphene, the electrode exhibited remarkable electrochemical performance with a high reversible capacity (≈1030 mA h g−1 after 60 cycles at 100 mA g−1), enhanced rate capability (≈970, ≈850, ≈555 mA h g−1 at 100, 500, 5000 mA g−1, respectively), and superior cyclic stability (≈805 mA h g−1 after 305 cycles at 2000 mA g−1 with a high coulombic efficiency of ≈99.5 %); these composites are thus high‐performance anode materials for lithium ion batteries.
High‐Capacity NiO–(Mesocarbon Microbeads) Conversion Anode for Lithium‐Ion Battery
Authors: Verrelli Roberta , Hassoun Jusef 
Published: April 2015

AbstractA conversion‐type, NiO–MCMB (mesocarbon microbeads) composite anode prepared by high‐energy ball milling is here characterized and tested in lithium half and full cells. An optimized and submicrometric morphology allows the NiO–MCMB electrode to achieve high cell performance and excellent rate capability, that is, delivering specific capacities of 515 and 450 mAh g−1 when cycled at current densities as high as 545 and 1090 mA g−1, respectively. The NiO–MCMB composite anode is studied in a full lithium‐ion battery using a high‐voltage LiNi0.5Mn1.5O4 electrode that is considered a suitable cathode in combination with conversion‐type electrodes. The battery delivers a specific capacity of 90 mAh g−1 with high coulombic efficiency and an average working voltage of 4.1 V. The electrochemical results suggest the viability of the alternative cell configuration here adopted for the development of low‐cost, high‐energy‐density lithium‐ion batteries.
Manganese Tetraboride, MnB4: High‐Temperature Crystal Structure, p–n Transition, 55Mn NMR Spectroscopy, Solid Solutions, and Mechanical Properties
Authors: Knappschneider Arno , Litterscheid Christian , Brgoch Jakoah , George Nathan C. , Henke Sebastian , Cheetham Anthony K. , Hu Jerry G. , Seshadri Ram , Albert Barbara 
Published: April 2015

AbstractThe structural and electronic properties of MnB4 were studied by high‐temperature powder X‐ray diffraction and measurements of the conductivity and Seebeck coefficient on spark‐plasma‐sintered samples. A transition from the room‐temperature monoclinic structure (space group P21/c) to a high‐temperature orthorhombic structure (space group Pnnm) was observed at about 650 K. The material remained semiconducting after the transition, but its behavior changed from p‐type to n‐type. 55Mn NMR measurements revealed an isotropic chemical shift of −1315 ppm, confirming an oxidation state of Mn close to I. Solid solutions of Cr1−xMnxB4 (two phases in space groups Pnnm and P21/c) were synthesized for the first time. In addition, nanoindentation studies yielded values of (496±26) and (25.3±1.7) GPa for the Young’s modulus and hardness, respectively, compared to values of 530 and 37 GPa obtained by DFT calculations.
Prediction of a Neutral Noble Gas Compound in the Triplet State
Authors: Manna Debashree , Ghosh Ayan , Ghanty Tapan K. 
Published: April 2015

AbstractDiscovery of the HArF molecule associated with HAr covalent bonding [Nature, 2000, 406, 874–876] has revolutionized the field of noble gas chemistry. In general, this class of noble gas compound involving conventional chemical bonds exists as closed‐shell species in a singlet electronic state. For the first time, in a bid to predict neutral noble gas chemical compounds in their triplet electronic state, we have carried out a systematic investigation of xenon inserted FN and FP species by using quantum chemical calculations with density functional theory and various post‐Hartree–Fock‐based correlated methods, including the multireference configuration interaction technique. The FXeP and FXeN species are predicted to be stable by all the computational methods employed in the present work, such as density functional theory (DFT), second‐order Møller–Plesset perturbation theory (MP2), coupled‐cluster theory (CCSD(T)), and multireference configuration interaction (MRCI). For the purpose of comparison we have also included the Kr‐inserted compounds of FN and FP species. Geometrical parameters, dissociation energies, transition‐state barrier heights, atomic charge distributions, vibrational frequency data, and atoms‐in‐molecules properties clearly indicate that it is possible to experimentally realize the most stable state of FXeP and FXeN molecules, which is triplet in nature, through the matrix isolation technique under cryogenic conditions.
Diborylated Magnesium Anthracene as Precursor for B2H5−‐Bridged 9,10‐Dihydroanthracene
Authors: Pospiech Steffen , Bolte Michael , Lerner Hans‐Wolfram , Wagner Matthias 
Published: April 2015

Abstract9,10‐(Bpin)2‐anthracene (3, HBpin=pinacolborane) was synthesized from 9,10‐dibromoanthracene in a stepwise lithiation/borylation sequence. The reaction of 3 with highly activated magnesium furnished the diborylated magnesium anthracene 4, which was quenched in situ with ethereal HCl to yield cis‐9,10‐(Bpin)2‐DHA (cis‐5, DHA=9,10‐dihydroanthracene). Compound cis‐5, in turn, can be reduced with Li[AlH4] in THF to give its diborate Li2[cis‐9,10‐(BH3)2‐DHA] (Li2[cis‐6]). In the crystal lattice, the THF solvate Li2[cis‐6]⋅3 THF establishes a dimeric structure with Li‐(μ‐H)‐B coordination modes. Hydride abstraction from Li2[cis‐6] with Me3SiCl yields the BHB‐bridged DHA Li[7]. This product can also be viewed as a unique cyclic B2H7− derivative with a hydrocarbon backbone. Treatment of Li2[cis‐6] with the stronger hydride abstracting agent Me3SiOTf (HOTf=trifluoromethanesulfonic acid) in THF affords the THF diadduct of cis‐9,10‐(BH(OTf))2‐DHA.
Phosphoester Hydrolysis: The Incoming Substrate Turns the Bridging Hydroxido Nucleophile into a Terminal One
Authors: Gouré Eric , Carboni Michaël , Troussier Angélique , Lebrun Colette , Pécaut Jacques , Jacquot Jean‐François , Dubourdeaux Patrick , Clémancey Martin , Blondin Geneviève , Latour Jean‐Marc 
Published: April 2015

AbstractIdentifying the active nucleophile in hydrolysis reactions catalyzed by binuclear hydrolases is a recurrent problem and a matter of intense debate. We report on the phosphate ester hydrolysis by a FeIIIFeII complex of a binucleating ligand. This complex presents activities in the range of those observed for similar biomimetic compounds in the literature. The specific electronic properties of the FeIIIFeII complex allowed us to use 1H NMR and Mössbauer spectroscopies to investigate the nature of the various species present in the solution in the pH range of 5–10. Both techniques showed that the hydrolysis activity is associated to a μ‐hydroxido FeIIIFeII species. Further 1H NMR experiments show that binding of anions or the substrate changes this bonding mode suggesting that a terminal hydroxide is the likely nucleophile in these hydrolysis reactions. This view is further supported by the structure determination of the hydrolysis product.
Exploiting the Brønsted Acidity of Phosphinecarboxamides for the Synthesis of New Phosphides and Phosphines
Authors: Jupp Andrew R. , Trott Gemma , Payen de la Garanderie Éléonore , Holl James D. G. , Carmichael Duncan , Goicoechea Jose M. 
Published: April 2015

AbstractWe demonstrate that the synthesis of new N‐functionalized phosphinecarboxamides is possible by reaction of primary and secondary amines with PCO− in the presence of a proton source. These reactions proceed with varying degrees of success, and although primary amines generally afford the corresponding phosphinecarboxamides in good yields, secondary amines react more sluggishly and often give rise to significant decomposition of the 2‐phosphaethynolate precursor. Of the new N‐derivatized phosphinecarboxamides available, PH2C(O)NHCy (Cy=cyclohexyl) can be obtained in sufficiently high yields to allow for the exploration of its Brønsted acidity. Thus, deprotonating PH2C(O)NHCy with one equivalent of potassium bis(trimethylsilyl)amide (KHMDS) gave the new phosphide [PHC(O)NHCy]−. In contrast, deprotonation with half of an equivalent gives rise to [P{C(O)NHCy}2]− and PH3. These phosphides can be employed to give new phosphines by reactions with electrophiles, thus demonstrating their enormous potential as chemical building blocks.
Carbon Anionic Chiral Initiators for Asymmetric Anionic Polymerization of Achiral Isocyanates
Authors: Hu Wei , Cao Jing , Huang Yi‐Ling , Liang Sai 
Published: April 2015

AbstractNovel optically active carbon anionic initiators bearing a chiral oxazole substituent on fluorene ring, (S)‐1‐(9H‐fluoren‐2‐yl)‐4‐isopropyl‐4, 5‐dihydrooxazole lithium ((S)‐1‐FIDD‐Li) and (S)‐2‐(9H‐fluoren‐2‐yl)‐4‐isopropyl‐4, 5‐dihydrooxazole lithium ((S)‐2‐FIDD‐Li), were synthesized. Anionic polymerizations of achiral polyisocyanates with the chiral initiators were investigated and optical rotation of the obtained polymers were attributed to asymmetric induction of the chiral initiators. The crowded substituent of initiator ((S)‐2‐FIDD‐Li) seems to reduce the polymerizability of isocyanates and yet enhances the chiral induced ability in polymerization. Chirality 27:449–453, 2015. © 2015 Wiley Periodicals, Inc.
A Risk Score for No Reflow in Patients With ST‐Segment Elevation Myocardial Infarction After Primary Percutaneous Coronary Intervention
Authors: Wang Jin‐Wen , Zhou Zi‐Qiang , Chen Yun‐Dai , Wang Chang‐Hua , Zhu Xiao‐ling 
Published: April 2015

ABSTRACTBackgroundMany factors are associated with no‐reflow (NRF) phenomenon in ST‐segment elevation myocardial infarction (STEMI), including plasma glucose, age, and pre–percutaneous coronary intervention (PCI) thrombus score. Initial clinical assessment would benefit from accurate NRF prediction. This study aimed to develop a simple scoring system to predict the risk of NRF in patients undergoing primary PCI with STEMI.MethodsBaseline clinical and procedural variables were used for risk score development (the training dataset, n = 912) and validation (the test dataset, n = 864). Independent predictors of NRF from the multivariable model were assigned integer weights based on their coefficients and incorporated into a risk score. The discriminant ability of the score was tested by receiver operating characteristic analysis using the test dataset.ResultsThe final model included 7 significant variables, which were age, pain‐to‐PCI time, neutrophil count, admission plasma glucose level, pre‐PCI thrombus score, collateral circulation, and Killip class. All these variables were then used to build a risk score in terms of the prediction of NRF. Receiver operating characteristic analysis demonstrated good risk prediction with a c statistic of 0.800 (95% confidence interval: 0.772‐0.826) in the test dataset.ConclusionsIn patients with STEMI treated by primary PCI, incidence of NRF phenomenon may be predicted with an acceptable accuracy based on a 7‐item simplified risk score.
Association of surgeon volume and hospital volume with the outcome of patients receiving definitive surgery for colorectal cancer: A nationwide population‐based study
Authors: Liu Chia‐Jen , Chou Yiing‐Jenq , Teng Chung‐Jen , Lin Chun‐Chi , Lee Yu‐Ting , Hu Yu‐Wen , Yeh Chiu‐Mei , Chen Tzeng‐Ji , Huang Nicole 
Published: April 2015

BACKGROUNDPatients with colorectal cancer (CRC) who undergo cancer surgeries with higher‐volume providers may have better outcomes. The current debate focuses on whether it is hospital volume or surgeon volume that matters more.METHODSThe authors conducted a nationwide population‐based study in Taiwan that enrolled all patients who underwent definitive surgery for newly diagnosed CRC between 2005 and 2011. All patients were divided into 4 quartiles according to hospital and surgeon volume. The main outcome was the 5‐year mortality rate, which was analyzed using a frailty model for Cox regression. The authors also conducted fixed and random effects multivariate regression models to examine short‐term outcomes and resource use, including operative mortality, hospital stay, emergency department visits within 30 days, and medical expenses. Analyses were adjusted for patient and provider characteristics.RESULTSA total of 61,728 patients with CRC were included in the current study. The 5‐year mortality rates were 38.7%, 32.8%, 32.0%, and 29.1% in descending order of hospital volume quartiles and were 41.4%, 34.1%, 29.8%, and 27.4% in descending order of surgeon volume quartiles. After adjustment for the individual and provider characteristics, surgeon volume, but not hospital volume, remained a significantly predictive factor of death (P<.001). In addition, those patients with CRC who underwent definitive surgeries performed by higher‐volume surgeons had a relatively lower risk of operative mortality, shorter hospital length of stay, and lower medical expenses.CONCLUSIONSPatients with CRC who underwent definitive surgery performed by higher‐volume providers were found to have better outcomes. Surgeon volume may play a more important role than hospital volume. Cancer 2015;121:2782‐2790. © 2015 American Cancer Society
How much do cancer‐related symptoms contribute to health‐related quality of life in lung and colorectal cancer patients? A report from the Cancer Care Outcomes Research and Surveillance (CanCORS) Consortium
Authors: Kenzik Kelly M. , Ganz Patricia A. , Martin Michelle Y. , Petersen Laura , Hays Ron D. , Arora Neeraj , Pisu Maria 
Published: April 2015

BACKGROUNDThe objective of this study was to examine associations of symptoms with physical and mental health‐related quality of life (HRQOL) in patients with colorectal cancer (CRC) and in patients with lung cancer.METHODSPatients with newly diagnosed CRC (n = 3040) or lung cancer (n = 2297) who were participating in the Cancer Care Outcomes Research and Surveillance Consortium study completed surveys on general HRQOL and symptoms. HRQOL was measured by using physical component summary (PCS) and mental component summary (MCS) scores on the Medical Outcomes Study 12‐item short‐form heath survey. Nonspecific cancer symptoms were measured using items from the European Organization for Research and Treatment of Cancer core quality‐of‐life questionnaire. Cancer type‐specific modules developed by the European Organization for Research and Treatment of Cancer were used to assess CRC‐specific and lung cancer‐specific symptoms. For both cancer types, linear regression models that were controlled for demographic and clinical information were used to examine correlations of nonspecific and cancer‐specific symptoms with PCS and MCS scores.RESULTSPCS scores for patients with CRC and lung cancer were below the general population norm of 50 (43 and 37, respectively), and MCS scores were at the population norm. For the CRC sample, in the model that included both symptom indices, an increase in nonspecific symptoms was more strongly associated with lower PCS and MCS scores than an increase in CRC‐specific symptoms (PCS, standardized coefficient [β] = −0.41 vs −0.09; MCS, β = −0.38 vs −0.08). In a similar model for lung cancer, increases in lung cancer‐specific symptoms were more strongly associated with lower PCS scores (β = −0.34 vs −0.20), whereas nonspecific symptoms were more strongly associated with lower MCS scores (β = −0.34 vs −0.14).CONCLUSIONSSymptoms were associated with HRQOL impairments in recently diagnosed patients. Additional supportive care implemented early in cancer care, regardless of cancer stage, may provide symptom relief and improve HRQOL Cancer 2015;121:2831‐2839. © 2015 American Cancer Society.
Prospective evaluation of p16/Ki‐67 dual‐stained cytology for managing women with abnormal Papanicolaou cytology: PALMS study results
Authors: Bergeron Christine , Ikenberg Hans , Sideri Mario , Denton Karin , Bogers Johannes , Schmidt Dietmar , Alameda Francisco , Keller Thomas , Rehm Susanne , Ridder Ruediger ,   for the PALMS Study Group
Published: April 2015

BACKGROUNDTesting for the presence of the human papillomavirus (HPV) is widely accepted for triaging Papanicolaou cytology results categorized as atypical squamous cells of undetermined significance (ASC‐US). In contrast, HPV testing has limited use in triaging cytological low‐grade squamous intraepithelial lesions (LSILs) due to prevalence rates of typically >80%. In the current study, the authors assessed the diagnostic performance of p16/Ki‐67 dual‐stained cytology in triaging ASC‐US and LSIL cases within the prospective, multicentric Primary ASC‐US LSIL Marker Study (PALMS).METHODSA total of 575 ASC‐US cases and 529 LSIL cases from a cohort of 27,349 women who were prospectively enrolled into the PALMS study in 5 European countries were tested with p16/Ki‐67 dual‐stained cytology and Hybrid Capture 2 (HC2) HPV testing. Colposcopy‐guided biopsy results of cervical intraepithelial neoplasia of grade 2 or worse (CIN2+) were used as clinical endpoints.RESULTSp16/Ki‐67 dual‐stained cytology demonstrated comparable (ASC‐US: 94.4% for dual‐stained cytology vs 100% for HC2 testing; P = .317) or lower (LSIL: 85.7% for dual‐stained cytology vs 98.4% for HC2 testing; P = .005) sensitivity for CIN2+, but higher levels of specificity compared with HC2 HPV testing in both ASC‐US (78.7% vs 60.4%; P<.001) and LSIL (53.3% vs 15.6%; P<.001) cases. Positive predictive values for CIN2+ were substantially higher for dual‐stained cytology versus HC2 HPV testing, especially in LSIL, and in ASC‐US cases for women aged <30 years.CONCLUSIONSThe clinical usefulness and efficiency of triaging women with ASC‐US or LSIL Papanicolaou cytology results by p16/Ki‐67 dual‐stained cytology testing has been confirmed in this prospective, pan‐European study. The high positive predictive value of dual‐stained cytology for the presence of high‐grade CIN may help to reduce the number of unnecessary colposcopy referrals. Cancer (Cancer Cytopathol) 2015;123:373–81. © 2015 American Cancer Society.
Sol‐to‐Gel Transition in Fast Evaporating Systems Observed by in Situ Time‐Resolved Infrared Spectroscopy
Authors: Innocenzi Plinio , Malfatti Luca , Carboni Davide , Takahashi Masahide 
Published: April 2015

AbstractThe in situ observation of a sol‐to‐gel transition in fast evaporating systems is a challenging task and the lack of a suitable experimental design, which includes the chemistry and the analytical method, has limited the observations. We synthesise an acidic sol, employing only tetraethylorthosilicate, SiCl4 as catalyst and deuterated water; the absence of water added to the sol allows us to follow the absorption from the external environment and the evaporation of deuterated water. The time‐resolved data, obtained by attenuated total reflection infrared spectroscopy on an evaporating droplet, enables us to identify four different stages during evaporation. They are linked to specific hydrolysis and condensation rates that affect the uptake of water from external environment. The second stage is characterized by a decrease in hydroxyl content, a fast rise of condensation rate and an almost stationary absorption of water. This stage has been associated with the sol‐to‐gel transition.
Negative Hyperconjugation versus Electronegativity: Vibrational Spectra of Free Fluorinated Alkoxide Ions in the Gas Phase
Authors: Oomens Jos , Berden Giel , Morton Thomas Hellman 
Published: April 2015

AbstractCO stretching frequencies of free, gaseous, fluorinated alkoxide ions shift substantially to the blue, relative to those of corresponding alcohols complexed with ammonia. Free α‐fluorinated ions, pentafluoroethoxide and heptafluoroisopropoxide anions, display further blue shifts relative to cases with only β‐fluorination, providing experimental evidence for fluorine negative hyperconjugation. DFT analysis with the atoms in molecules (AIM) method confirms an increase in CO bond order for the α‐fluorinated ions, demonstrating an increase in carbonyl character for the free ions.
Sub‐Bandgap Excitation‐Induced Electron Injection from CdSe Quantum Dots to TiO2 in a Directly Coupled System
Authors: Yoshii Mari , Kobayashi Hisayoshi , Tada Hiroaki 
Published: April 2015

AbstractWe show that the sub‐bandgap excitation of a directly coupled CdSe quantum dot (QD)–TiO2 system induces electron injection from CdSe levels to the conduction band of TiO2, leading to spectral extension of the light response. We anticipate that this study presents a useful guideline for improving the conversion efficiency of QD‐sensitized solar cells.
Vacuum Surface Science Meets Heterogeneous Catalysis: Dehydrogenation of a Liquid Organic Hydrogen Carrier in the Liquid State
Authors: Matsuda Takashi , Taccardi Nicola , Schwegler Johannes , Wasserscheid Peter , Steinrück Hans‐Peter , Maier Florian 
Published: April 2015

AbstractUltrahigh vacuum (UHV) surface science techniques are used to study the heterogeneous catalytic dehydrogenation of a liquid organic hydrogen carrier in its liquid state close to the conditions of real catalysis. For this purpose, perhydrocarbazole (PH), otherwise volatile under UHV, is covalently linked as functional group to an imidazolium cation, forming a non‐volatile ionic liquid (IL). The catalysed dehydrogenation of the PH unit as a function of temperature is investigated for a Pt foil covered by a macroscopically thick PH‐IL film and for Pd particles suspended in the PH‐IL film, and for PH‐IL on Au as inert support. X‐ray photoelectron spectroscopy and thermal desorption spectroscopy allows us to follow in situ the catalysed transition of perhydrocarbazole to carbazole at technical reaction temperatures. The data demonstrate the crucial role of the Pt and Pd catalysts in order to shift the dehydrogenation temperature below the critical temperature of thermal decomposition.