bluuebunny/crossref_metadata_2025_split huggingface dataset:
Effect of Hexafluorophosphate and Fluoroethylene Carbonate on Electrochemical Performance and the Surface Layer of Hard Carbon for Sodium‐Ion Batteries
Authors: Dahbi Mouad , Nakano Takeshi , Yabuuchi Naoaki , Fujimura Shun , Chihara Kuniko , Kubota Kei , Son Jin‐Young , Cui Yi‐Tao , Oji Hiroshi , Komaba Shinichi 
Published: August 2016

AbstractElectrochemical sodium insertion for hard carbon is examined in a cyclic alkylene carbonate based solution containing a NaClO4 or NaPF6 salt with a fluoroethylene carbonate (FEC) additive to study electrolyte dependency for sodium‐ion batteries. NaPF6‐based electrolytes provide superior reversibility and cyclability of sodium insertion into hard carbon compared with NaClO4‐based ones. The FEC‐derived passivation film improves capacity retention because of better passivation with a thinner surface layer, as revealed by hard and soft X‐ray photoelectron spectroscopy (PES). The use of both the NaPF6 salt and FEC additive results in a synergetic effect on passivation for the hard‐carbon electrode, leading to enhanced cycle performance. Hard‐carbon electrodes with polyvinylidene difluoride binder in propylene carbonate based electrolytes containing NaPF6 and FEC demonstrate excellent capacity retention with a reversible capacity of about 250 mAh g−1. The difference in capacity retention for the electrolytes is expected to originate as a consequence of the difference in the surface interphase layer formed on the hard‐carbon electrodes. Surface analyses with PES and time‐of‐flight secondary ion mass spectrometry reveal differences in surface and passivation chemistry which depend on the salts, solvents, and FEC additives used for the hard‐carbon negative electrodes.
Electrocontrolled Swelling and Water Uptake of a Three‐Dimensional Conducting Polypyrrole Hydrogel
Authors: Antonio Jadielson L. , Höfler Lajos , Lindfors Tom , Córdoba de Torresi Susana I. 
Published: August 2016

AbstractPolypyrrole 3D hydrosponges of tubular structure were synthesized and electrochemically characterized. The Fourier transform infrared attenuated total reflection (FTIR‐ATR) spectroscopy technique was employed to study the water uptake of the hydrosponges under different conditions. This technique presents several advantages over conventional swelling measurements due to its specificity that allows analyzing the kinetics of water uptake at the molecular level. In combination with mathematical modeling, FTIR‐ATR spectroscopy also enables the calculation of the water diffusion coefficients in the hydrogels. The experimental setup also allows electroswelling of the hydrosponges to be studied. The results presented herein are complementary to those obtained with the electrochemical quartz crystal microbalance with dissipation (EQCM‐D) technique and make it possible to determine the actual role played by water in the ionic exchange occurring in conducting polymers during their redox processes. Whereas EQCM‐D shows the whole mass change in the film provoked by injection/ejection of ions and solvent molecules, FTIR‐ATR spectroscopy follows water flux only, which thus allows separation of the solvent contribution.
Colloidal Surface Active Maghemite Nanoparticles for Biologically Safe CrVI Remediation: from Core‐Shell Nanostructures to Pilot Plant Development
Authors: Magro Massimiliano , Domeneghetti Stefania , Baratella Davide , Jakubec Petr , Salviulo Gabriella , Bonaiuto Emanuela , Venier Paola , Malina Ondřej , Tuček Jiří , Ranc Václav , Zoppellaro Giorgio , Zbořil Radek , Vianello Fabio 
Published: August 2016

AbstractThe present study is aimed at the exploration of achievable improvements for CrVI ex situ and in situ water remediation by using novel naked colloidal maghemite (γ‐Fe2O3) nanoparticles (surface active maghemite nanoparticles, SAMNs). The reliability of SAMNs for CrVI binding and removal was demonstrated, and SAMN@CrVI complex was characterized, as well as the covalent nature of the absorption was unequivocally proved. SAMNs were structurally and magnetically well conserved after CrVI binding. Thus, in consideration of their affinity for CrVI, SAMNs were exploited in a biological model system, mimicking a real in situ application. The assay evidenced a progressive reduction of revertant colonies of Salmonella typhimurium TA100 strain, as maghemite nanoparticles concentration increased, till the complete suppression of CrVI mutagen effect. Finally, an automatic modular pilot system for continuous magnetic removal and recovery of CrVI from water is proposed. SAMNs, thanks to their colloidal, binding, and catalytic properties, represent a promising tool as a reliable nanomaterial for water remediation by CrVI.
Ferroelectric Coordination Polymers Self‐Assembled from Mesogenic Zinc(II) Porphyrin and Dipolar Bridging Ligands
Authors: Hui Joseph K.‐H. , Kishida Hiroyuki , Ishiba Keita , Takemasu Kenta , Morikawa Masa‐aki , Kimizuka Nobuo 
Published: August 2016

AbstractA new class of ferroelectric coordination‐based polymers has been developed by the self‐assembly of lipophilic zinc porphyrin (ZnP) and ditopic bridging ligands. The ligands contain dipolar benzothiadiazole or fluorobenzene units, which are axially coordinated to ZnP with the dipole moments oriented perpendicular to the coordination axes. The coordination‐based polymers show ferroelectric characteristics in the liquid crystalline state, as revealed by distinctive hysteresis in the polarization–electric field (P–E) loops and inversion current peaks in current–voltage (I–V) loops. The observed ferroelectric properties are explainable by flip–flop rotation of the dipolar axle ligands induced by the applied electric field, as demonstrated by the positive‐up–negative‐down (PUND) measurements. The present system provides a new operating principle in supramolecular ferroelectrics.
Towards Polysulfuric Acids: The Hydrogentrisulfate Anion [HS3O10]− in A[HS3O10] (A=Na, K, Rb)
Authors: Schindler Lisa Verena , Klüner Thorsten , Wickleder Mathias S. 
Published: August 2016

AbstractThe reaction of Na2SO4 and K2SO4 with fuming sulfuric acid (65 % SO3) yielded colorless extremely sensitive crystals of Na[HS3O10] (monoclinic; P21/n (No. 14); Z=4; a=707.36(2), b=1378.56(4), c=848.10(3) pm; β=94.817(1)°; V=824.09(4)⋅106 pm3) and K[HS3O10] (orthorhombic; Pccn (No. 56); Z=4; a=1057.16(3), b=807.81(2), c=897.57(2) pm; V=766.51(3)⋅106 pm3). The analogous rubidium compound Rb[HS3O10] (orthorhombic; Pnma (No. 62); Z=4; a=891.43(3), b=1095.34(4), c=839.37(3) pm; V=819.58(5)⋅106 pm3) originates from the reaction of Rb2CO3 and SO3. All of the different structures contain the hitherto unknown anion [HS3O10]− and are stamped by strong hydrogen bonds linking the anions either to dimers or chains. Theoretical investigations by DFT methods give further insight in the structural characteristics of [HS3O10]−. The preparation of the [HS3O10]− anion can be seen as an important milestone on our way to the still elusive polysulfuric acids.
Characterization of Tetracyanopyridine (TCNPy)‐Based Magnets: V[TCNPy]2⋅z (CH2Cl2) (Tc=111 K) and V[TCNPy]3⋅z (CH2Cl2) (Tc=90 K)
Authors: Hao Jingjun , Davidson Royce A. , Kareis Christopher M. , Kavand Marzieh , van Schooten Kipp J. , Boehme Christoph , Wöß Eva , Knör Günther , Miller Joel S. 
Published: August 2016

AbstractThe reaction of 2,3,5,6‐tetracyanopyridine (TCNPy) with V(CO)6 in CH2Cl2 forms new organic‐based magnets of V[TCNPy]x⋅z (CH2Cl2) (x=2, 3) composition. Analysis of the IR spectra suggests that the TCNPy is reduced and coordinated to VII sites through the nitriles. V[TCNPy]x order as ferrimagnets with 111 and 90 K Tc values for V[TCNPy]2 and V[TCNPy]3, respectively. Their respective remanent magnetizations and coercive fields are 1260 and 250 emuOe mol−1 and 9 and 6 Oe at 5 K, and they exhibit some spin‐glass behavior.
Asymmetric Total Synthesis of (−)‐Erogorgiaene and Its C‐11 Epimer and Investigation of Their Antimycobacterial Activity
Authors: Incerti‐Pradillos Celia A. , Kabeshov Mikhail A. , O'Hora Paul S. , Shipilovskikh Sergei A. , Rubtsov Aleksandr E. , Drobkova Vera A. , Balandina Svetlana Yu. , Malkov Andrei V. 
Published: August 2016

AbstractA short, nine‐step, highly enantioselective synthesis of (−)‐erogorgiaene and its C‐11 epimer is reported. The key stereochemistry controlling steps involve catalytic asymmetric crotylation, anionic oxy‐Cope rearrangement and cationic cyclisation. (−)‐Erogorgiaene exhibited promising antitubercular activity against multidrug‐resistant strains of Mycobacterium tuberculosis.
Electrochemical Oxidative C−H/N−H Coupling between γ‐Lactams and Anilines
Authors: Gong Ming , Huang Jing‐Mei 
Published: August 2016

AbstractA mild method for the direct C−H/N−H coupling between γ‐lactams and anilines through electrochemical oxidation has been developed. The protocol proceeded smoothly without metal catalysts at room temperature to afford γ‐substituted γ‐lactams in good yields. It has been revealed that the quasi‐divided cell which provided high current density on the anode was crucial for this reaction.
Mild Amide‐Cleavage Reaction Mediated by Electrophilic Benzylation
Authors: Yamada Kohei , Karuo Yukiko , Tsukada Yuichi , Kunishima Munetaka 
Published: August 2016

AbstractAn extremely mild method for amide‐cleavage by using the triazine‐based benzylating reagent 4‐(4,6‐diphenoxy‐1,3,5‐triazin‐2‐yl)‐4‐benzylmorpholinium trifluoromethanesulfonate (DPT‐BM), which spontaneously releases benzyl cation species when being dissolved at room temperature, has been developed. O‐Benzylation of the amide with DPT‐BM and the subsequent hydrolysis of the resulting intermediate benzyl imidate salt afford the corresponding amine and benzyl ester, which can be converted by hydrogenolysis into a carboxylic acid under neutral conditions. O‐Benzylation proceeds depending on both steric and electronic factors around the amide group. Thus, some amides have been selectively cleaved over other amides. Furthermore, intramolecular chemoselective cleavage of an amide group in the presence of an ester group was achieved. Such selective hydrolytic reactions cannot be performed with Meerwein reagents as well as under acidic or basic hydrolytic conditions.
Trace Determination and Pressure Estimation of Fluorine F2 Caused by Irradiation Damage in Minerals and Synthetic Fluorides
Authors: Celinski Vinicius R. , Ditter Michael , Kraus Florian , Fujara Franz , Schmedt auf der Günne Jörn 
Published: August 2016

AbstractIrradiated alkali and earth alkali halides can form metal colloids and halogen molecules, which stay trapped inside the crystal. In this paper we provide 19F NMR spectroscopic evidence of trapped F2 fluids in heavy ion‐bombarded synthesized LiF crystals as well as in a variety of the mineral Villiaumite (NaF). This is the 2nd mineral in which F2 is unambiguously detected in nature. The trace quantification of the latter is in the order of magnitude of 10−6 mol g−1. Pressures and densities of the F2 fluids are estimated based on the theory of nuclear spin relaxation in dilute gases.
Changes in cytogenetics and molecular genetics in acute myeloid leukemia from childhood to adult age groups
Authors: Creutzig Ursula , Zimmermann Martin , Reinhardt Dirk , Rasche Mareike , von Neuhoff Christine , Alpermann Tamara , Dworzak Michael , Perglerová Karolína , Zemanova Zuzana , Tchinda Joelle , Bradtke Jutta , Thiede Christian , Haferlach Claudia 
Published: August 2016

BACKGROUNDTo obtain better insight into the biology of acute myeloid leukemia (AML) in various age groups, this study focused on the genetic changes occurring during a lifetime.METHODSThis study analyzed the relation between age and genetics from birth to 100 years in 5564 patients with de novo AML diagnosed from 1998 to 2012 (1192 patients from nationwide pediatric studies [AML Berlin‐Frankfurt‐Münster studies 98 and 2004] and 4372 adults registered with the Munich Leukemia Laboratory).RESULTSThe frequencies of cytogenetic subgroups were age‐dependent. Favorable subtypes (t(8;21), inv(16)/t(16;16), and t(15;17)) decreased in general from the pediatric age group (2 to < 18 years; 33%) to the oldest groups (<5% for > 70 years; P < .0001). Unfavorable cytogenetics (–7/del(7), –5/del(5q) or 5p, inv(3)/t(3;3), t(6;9), complex karyotype, 12p, 17p, and 11q23/mixed‐lineage leukemia aberrations, excluding t(9;11)) were frequent (42%) in infants (<2 years), had a low frequency in children and young adults (<22%), and increased in frequency up to 36% in patients older than 85 years (P = .01). This was even more significant for complex karyotypes (P ≤ .0001), which also showed a strong increase in the absolute age‐specific incidence with age. Interestingly, the frequency of 11q23 abnormalities decreased from infants to older patients. The proportion of clinically relevant molecular aberrations of CCAAT/enhancer binding protein α, nucleophosmin (NPM1), and NPM1/fms‐related tyrosine kinase 3–internal tandem duplication increased with age.CONCLUSIONSAltogether, with the exclusion of infants, a significant decrease in the proportion of favorable cytogenetic subtypes and an increase in unfavorable cytogenetics were observed with increasing age. These findings indicate different mechanisms for the pathogenesis of AML; these different mechanisms also suggest directions for etiological research and contribute to the more unfavorable prognosis with increasing age. Cancer 2016;122:3821–3830. © 2016 American Cancer Society.
Family‐based exome‐wide assessment of maternal genetic effects on susceptibility to childhood B‐cell acute lymphoblastic leukemia in hispanics
Authors: Archer Natalie P. , Perez‐Andreu Virginia , Scheurer Michael E. , Rabin Karen R. , Peckham‐Gregory Erin C. , Plon Sharon E. , Zabriskie Ryan C. , De Alarcon Pedro A. , Fernandez Karen S. , Najera Cesar R. , Yang Jun J. , Antillon‐Klussmann Federico , Lupo Philip J. 
Published: August 2016

BACKGROUNDChildren of Hispanic ancestry have a higher incidence of acute lymphoblastic leukemia (ALL) compared with other ethnic groups, but to the authors' knowledge, the genetic basis for these racial disparities remain incompletely understood. Genome‐wide association studies of childhood ALL to date have focused on inherited genetic effects; however, maternal genetic effects (the role of the maternal genotype on phenotype development in the offspring) also may play a role in ALL susceptibility.METHODSThe authors conducted a family‐based exome‐wide association study of maternal genetic effects among Hispanics with childhood B‐cell ALL using the Illumina Infinium HumanExome BeadChip. A discovery cohort of 312 Guatemalan and Hispanic American families and an independent replication cohort of 152 Hispanic American families were used.RESULTSThree maternal single‐nucleotide polymorphisms (SNPs) approached the study threshold for significance after correction for multiple testing (P<1.0 × 10−6): MTL5 rs12365708 (testis expressed metallothionein‐like protein [tesmin]) (relative risk [RR], 2.62; 95% confidence interval [95% CI], 1.61‐4.27 [P = 1.8 × 10−5]); ALKBH1 rs6494 (AlkB homolog 1, histone H2A dioxygenase) (RR, 3.77; 95% CI, 1.84‐7.74 [P = 3.7 × 10−5]); and NEUROG3 rs4536103 (neurogenin 3) (RR, 1.75; 95% CI, 1.30‐2.37 [P = 1.2 × 10−4]). Although effect sizes were similar, these SNPs were not nominally significant in the replication cohort in the current study. In a meta‐analysis comprised of the discovery cohort and the replication cohort, these SNPs were still not found to be statistically significant after correction for multiple comparisons (rs12365708: pooled RR, 2.27 [95% CI, 1.48‐3.50], P = 1.99 × 10−4; rs6494: pooled RR, 2.31 [95% CI, 1.38‐3.85], P = .001; and rs4536103: pooled RR, 1.67 [95% CI, 1.29‐2.16] P = 9.23 × 10−5).CONCLUSIONSIn what to the authors' knowledge is the first family‐based based exome‐wide association study to investigate maternal genotype effects associated with childhood ALL, the results did not implicate a strong role of maternal genotype on disease risk among Hispanics; however, 3 maternal SNPs were identified that may play a modest role in susceptibility. Cancer 2016;122:3697‐704. © 2016 American Cancer Society.
A novel prognostic model for osteosarcoma using circulating CXCL10 and FLT3LG
Authors: Flores Ricardo J. , Kelly Aaron J. , Li Yiting , Nakka Manjula , Barkauskas Donald A. , Krailo Mark , Wang Lisa L. , Perlaky Laszlo , Lau Ching C. , Hicks M. John , Man Tsz‐Kwong 
Published: August 2016

BACKGROUNDOsteosarcoma (OS) is the most common malignant pediatric bone tumor. The identification of novel biomarkers for early prognostication will facilitate risk‐based stratification and therapy. This study investigated the significance of circulating cytokines/chemokines for predicting the prognosis at the initial diagnosis.METHODSLuminex assays were used to measure cytokine/chemokine concentrations in blood samples from a discovery cohort of OS patients from Texas Children's Hospital (n = 37) and an independent validation cohort obtained from the Children's Oncology Group (n = 233). After the validation of the biomarkers, a multivariate model was constructed to stratify the patients into risk groups.RESULTSThe circulating concentrations of C‐X‐C motif chemokine ligand 10 (CXCL10), Fms‐related tyrosine kinase 3 ligand (FLT3LG), interferon γ (IFNG), and C‐C motif chemokine ligand 4 (CCL4) were significantly associated with overall survival in both cohorts. Among these candidates, CXCL10 and FLT3LG were independent of the existing prognostic factor, metastasis at diagnosis, and CCL4 further discriminated cancer cases from controls. CXCL10, FLT3LG, and the metastatic status at diagnosis were combined to develop a multivariate model that significantly stratified the patients into 4 distinct risk groups (P = 1.6 × 10−8). The survival analysis showed that the 5‐year overall survival rates for the low‐, intermediate‐, high‐, and very high–risk groups were 77%, 54%, 47%, and 10%, respectively, whereas the 5‐year event‐free survival rates were 64%, 47%, 27%, and 0%, respectively. Neither CXCL10 nor FLT3LG tumor expression was significantly associated with survival.CONCLUSIONSHigh circulating levels of CXCL10 and FLT3LG predicted worse survival for patients with OS. Because both CXCL10 and FL3LG axes are potentially targetable, further study may lead to novel risk‐based stratification and therapy for OS. Cancer 2017;144–154. © 2016 American Cancer Society.
Inclusion of Ethyl Acetoacetate Bearing 7‐Hydroxycoumarin Dye by β‐Cyclodextrin and its Cooperative Assembly with Mercury(II) Ions: Spectroscopic and Molecular Modeling Studies
Authors: Aliaga Margarita E. , Fierro Angélica , Uribe Iván , García‐Río Luis , Cañete Álvaro 
Published: August 2016

AbstractThe inclusion of the fluorescent organic dye, ethyl 3‐(7‐hydroxy‐2‐oxo‐2H‐chromen‐3‐yl)‐3‐oxopropanoate (1) by the host β‐cyclodextrin (β‐CD), and its response toward mercuric ions (Hg2+), was studied by UV/Vis, fluorescence, and 1H NMR spectroscopic analyses, mass spectrometry and molecular modeling studies. 1H NMR measurements together with molecular modeling studies for dye 1 demonstrate that it exhibits two tautomeric forms (keto and enol); however, when the dye is included into the β‐CD cavity, the enol form predominates. Moreover, by using spectroscopic and spectrometry techniques, a 1:1 stoichiometry was determined for the complexes formed between dye 1 (enol form) and β‐CD, with a binding constant (Kb1=1.8×104 m−1) and for the dye 1 (keto form)‐Hg2+ (Kb2=2.3×103 m−1). Interestingly, in the presence of 1–β‐CD complex and mercuric ions, a ternary supramolecular system (Hg–1–β‐CD complex) was established, with a 1:1:1 stoichiometry and a Kb3 value of 4.3×103 m−1, with the keto form of the dye being the only one present in this assembly. The three‐component system provides a starting point for the development of novel and directed supramolecular assemblies.
Spatially Heterogeneous Nature of Self‐Catalytic Reaction in Hetero‐Double Helix Formation of Helicene Oligomers
Authors: Kushida Yo , Sawato Tsukasa , Saito Nozomi , Shigeno Masanori , Satozono Hiroshi , Yamaguchi Masahiko 
Published: August 2016

AbstractA 1:1 mixture of pseudoenantiomeric aminomethylenehelicene oligomers, (P)‐tetramer and (M)‐pentamer, in fluorobenzene show a self‐catalytic phenomenon in the formation of hetero‐double helices from random coils. This study visualizes the spatially heterogeneous nature of the self‐catalytic reaction in dilute solution. UV/Vis imaging analysis of the mixture at 70 °C, containing random coils, exhibits a homogeneous bright area. When the solution is cooled from 70 to 30 °C and held at that temperature, dark domains of approximately 1 mm in size appear, which move approximately at a rate of 1 mm min−1. The dark domains indicate that weaker UV/Vis absorption results from the formation of hetero‐double helices, which is supported by circular dichroism (CD) imaging experiments. Then a homogeneous mixture is regenerated upon heating to 55 °C, as shown by CD imaging. Under self‐catalytic conditions, a homogeneous solution spontaneously changed to a heterogeneous solution in the process of hetero‐double‐helix formation.
Masked N‐Heterocyclic Carbene‐Catalyzed Alkylation of Phenols with Organic Carbonates
Authors: Lui Matthew Y. , Yuen Alexander K. L. , Masters Anthony F. , Maschmeyer Thomas 
Published: August 2016

AbstractAn easily prepared masked N‐heterocyclic carbene, 1,3‐dimethylimidazolium‐2‐carboxylate (DMI‐CO2), was investigated as a “green” and inexpensive organocatalyst for the alkylation of phenols. The process made use of various low‐toxicity and renewable alkylating agents, such as dimethyl‐ and diethyl carbonate, in a focused microwave reactor. DMI‐CO2 was found to be a very active catalyst and excellent yields of a range of aryl alkyl ethers were obtained under relatively benign conditions. The observed difference in the conversion behavior of phenol methylation, in the presence of either the carbene or 1,8‐diazabicycloundec‐7‐ene (DBU) catalyst, was rationalized on the basis of mechanistic investigations. The primary mode of action for the N‐heterocyclic carbene is nucleophilic catalysis. Activation of the dialkyl carbonate electrophile results in concomitant evolution of an organo‐soluble alkoxide, which deprotonates the phenolic starting material. In contrast, DBU is initially protonated by the phenol and thus consumed. Subsequent regeneration and participation in nucleophilic catalysis only becomes significant after some phenolate alkylation occurs.
Shear tests on external clay unit masonry walls / Monolithische Ziegelaußenwände unter Schubbeanspruchung
Authors: Kranzler Thomas 
Published: August 2016

AbstractMonolithic external walls are commonly made of thermally insulated clay blocks that do not require any additional external thermal insulation such as an external thermally insulated composite system (ETICS). To reduce thermal bridge losses, the support length (a) of the slab on the wall is shorter than the wall thickness (t): a < t. The influence on the shear capacity of the respective masonry walls has not yet been tested and analysed. The paper presents the results of shear tests on monolithic external walls with a reduced support length under static‐cyclic and pseudo‐dynamic loading. The test results will be compared with the shear resistance calculated according to DIN EN 1996 with consideration of the German National Annex and the results according to the relevant Technical Approval.