bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synthesis and Isolation of the Titanium–Scandium Endohedral Fullerenes—Sc2TiC@Ih‐C80, Sc2TiC@D5h‐C80and Sc2TiC2@Ih‐C80: Metal Size Tuning of the TiIV/TiIIIRedox Potentials
Authors: Junghans Katrin , Ghiassi Kamran B. , Samoylova Nataliya A. , Deng Qingming , Rosenkranz Marco , Olmstead Marilyn M. , Balch Alan L. , Popov Alexey A. 
Published: July 2016

AbstractThe formation of endohedral metallofullerenes (EMFs) in an electric arc is reported for the mixed‐metal Sc–Ti system utilizing methane as a reactive gas. Comparison of these results with those from the Sc/CH4and Ti/CH4systems as well as syntheses without methane revealed a strong mutual influence of all key components on the product distribution. Whereas a methane atmosphere alone suppresses the formation of empty cage fullerenes, the Ti/CH4system forms mainly empty cage fullerenes. In contrast, the main fullerene products in the Sc/CH4system are Sc4C2@C80(the most abundant EMF from this synthesis), Sc3C2@C80, isomers of Sc2C2@C82, and the family Sc2C2 n(2 n=74, 76, 82, 86, 90, etc.), as well as Sc3CH@C80. The Sc–Ti/CH4system produces the mixed‐metal Sc2TiC@C2 n(2 n=68, 78, 80) and Sc2TiC2@C2 n(2 n=80) clusterfullerene families. The molecular structures of the new, transition‐metal‐containing endohedral fullerenes, Sc2TiC@Ih‐C80, Sc2TiC@D5h‐C80, and Sc2TiC2@Ih‐C80, were characterized by NMR spectroscopy. The structure of Sc2TiC@Ih‐C80was also determined by single‐crystal X‐ray diffraction, which demonstrated the presence of a short Ti=C double bond. Both Sc2TiC‐ and Sc2TiC2‐containing clusterfullerenes have Ti‐localized LUMOs. Encapsulation of the redox‐active Ti ion inside the fullerene cage enables analysis of the cluster–cage strain in the endohedral fullerenes through electrochemical measurements.
Towards an Observation of Active Conformations in Asymmetric Catalysis: Interaction‐Induced Conformational Preferences of a Chiral Thiourea Model Compound
Authors: Kreienborg Nora M. , Pollok Corina H. , Merten Christian 
Published: July 2016

AbstractThe observation of the active species is the goal of most spectroscopic investigations on enantioselective organocatalysts in solution. Although NMR spectroscopy is widely applied, it has low sensitivity for conformational changes or the chiral nature of the interactions. In the present work, we exemplify the use of vibrational circular dichroism (VCD) spectroscopy for the characterization of a chiral thiourea model compound in nonpolar and polar solvents, as well as for a detailed analysis of its interaction with a model reactant. We discuss solvent‐induced conformational changes of the thiourea, and provide evidence for an unexpected binding topology between the thiourea and an acetate anion. The results clearly showcase the possibilities offered by using VCD spectroscopy in the characterization of chiral organocatalysts.
In Situ Generation of CoIII–Salen Complexes for Copolymerization of Propylene Oxide and CO2
Authors: Hatazawa Masahiro , Nakabayashi Koji , Ohkoshi Shin‐ichi , Nozaki Kyoko 
Published: July 2016

AbstractA simple admixture of CoII–salcy complexes with [Cp2FeIII]PF6 resulted in reproduction of the results with isolated CoIII–salcy complexes in the copolymerization of epoxide and carbon dioxide. By using this in situ‐generated active species with bis(triphenylphosphoranilydene)ammonium 2,4‐dinitrophenolate, a para‐methoxy‐substituted Co–salcy complex was proven to be more active than the parent tert‐butyl‐substituted system. In contrast, the CoII–salcy complex substituted with the more strongly electron‐donating NMe2 group did not show any activity for this copolymerization.
Oxidative Annulation of Arenecarboxylic and Acrylic Acids with Alkynes under Ambient Conditions Catalyzed by an Electron‐Deficient Rhodium(III) Complex
Authors: Kudo Eiji , Shibata Yu , Yamazaki Mutsumi , Masutomi Koji , Miyauchi Yuta , Fukui Miho , Sugiyama Haruki , Uekusa Hidehiro , Satoh Tetsuya , Miura Masahiro , Tanaka Ken 
Published: July 2016

AbstractIt has been established that an electron‐deficient CpE rhodium(III) complex catalyzes the oxidative [4+2] annulation of substituted arenecarboxylic and acrylic acids with alkynes under ambient conditions (at RT–40 °C, under air) without using excess amounts of substrates to produce the corresponding substituted isocoumarins and α‐pyrones in high yields. Minor modification of reaction conditions depending on the coordination ability of alkynes realized the high efficiency.
Randomized phase 2 trial of a coordinated breast cancer follow‐up care program
Authors: Ruddy Kathryn J. , Guo Hao , Baker Emily L. , Goldstein Matthew J. , Mullaney Erin E. , Shulman Lawrence N. , Partridge Ann H. 
Published: July 2016

BACKGROUNDPrevious research has demonstrated that cancer survivors often fail to receive recommended care and also undergo unnecessary care; this reduces care quality and increases costs.METHODSThis phase 2 trial randomized 100 stage 0 to IIIa breast cancer patients who had primary care providers within a large Massachusetts‐based hospital network (with accessible online records) to either coordinated follow‐up care (CC), which entailed a tailored survivorship care plan (SCP) and patient navigator calls every 3 months, or standard care (SC), which did not include an SCP or patient navigation, for 1 year after the completion of their last chemotherapy, surgery, or radiation treatment. The primary endpoint was the frequency of redundant examinations (>1 breast/chest wall examination per patient within any 30‐day period in the absence of a new breast or chest wall complaint) over the year of follow‐up. The total number of non–plastic surgery visits in the year of follow‐up was a secondary endpoint.RESULTSTwo patients (both on CC) were ineligible, and 2 patients (1 per arm) had a recurrence or died during follow‐up; this left 96 for analysis (47 in the CC arm and 49 in the SC arm). Twenty‐two of the 47 CC patients (47%; 95% confidence interval, 32%‐62%) and 19 of the 49 SC patients (39%; 95% confidence interval, 25%‐54%) had 1 or more redundant breast/chest wall examinations during the year. The median number of non–plastic surgery visits was 12 for CC patients and 8 for SC patients.CONCLUSIONSEarly‐stage breast cancer patients visit health care providers very frequently during their first year of follow‐up and often receive unnecessary breast/chest wall examinations. An SCP and patient navigator calls did not reduce this surrogate for redundant care. Cancer 2016;122:3546–3554. © 2016 American Cancer Society
Is Regioselectivity in the Enzyme‐Catalyzed Hydroperoxidation of Arachidonic Acid Necessarily Determined by Hydrogen Abstraction? The Case of Rabbit Leu597Ala/Ile663Ala ALOX15 Mutant
Authors: Saura Patricia , Masgrau Laura , Heydeck Dagmar , Kühn Hartmut , Lluch José M. , González‐Lafont Àngels 
Published: July 2016

AbstractMolecular dynamics simulations and quantum mechanics/molecular mechanics calculations were performed on the in silico Leu597Ala/Ile663Ala double mutant of rabbit ALOX15 (12/15 lipoxygenase). The computational results suggested that subtle steric hindrance by the conserved Leu597 and C‐terminal Ile663 residues disturbed H10 abstractions in wildtype ALOX15 (which abstracts H13), but if these two bulky residues were mutated to smaller ones, H10 abstraction was no longer impeded and the regioselectivity of the initial H‐abstraction step was changed. However, site‐directed mutagenesis with HPLC analysis of the products of the whole oxidation process showed that the regioselectivity of the hydroperoxidation was not altered. This disagreement may be explained by the conformational reorganization of the system needed to rotate the −OO. group from an antarafacial to a suprafacial arrangement prior to back‐hydrogen transfer. After H10 abstraction and O2 insertion, the evolution of the peroxy radical at C12 was sterically impeded, whereas peroxyl group rotation at C15 (after H13 abstraction) could easily evolve to a suprafacial arrangement, which thus led to the final product. For this reason, the global regiospecificity was not affected in the mutant. These findings exemplify that the regioselectivity of initial hydrogen abstraction and the regioselectivity of the final product do not necessarily coincide (in fact, they can be opposite) for the hydroperoxidation of arachidonic acid catalyzed by a lipoxygenase.
Efficient Batch‐Mode Parahydrogen‐Induced Polarization of Propane
Authors: Salnikov Oleg G. , Barskiy Danila A. , Coffey Aaron M. , Kovtunov Kirill V. , Koptyug Igor V. , Chekmenev Eduard Y. 
Published: July 2016

AbstractWe report on a simple approach for efficient NMR proton hyperpolarization of propane using the parahydrogen‐induced polarization (PHIP) technique, which yielded ≈6.2 % proton polarization using ≈80 % parahydrogen, a record level achieved with any hyperpolarization technique for propane. Unlike in previously developed approaches designed for continuous‐flow operation, where reactants (propene and parahydrogen) are simultaneously loaded for homogeneous or heterogeneous pairwise addition of parahydrogen, here a batch‐mode method is applied: propene is first loaded into the catalyst‐containing solution, which is followed by homogeneous hydrogenation via parahydrogen bubbling delivered at ≈7.1 atm. The achieved nuclear spin polarization of this contrast agent potentially useful for pulmonary imaging is approximately two orders of magnitude greater than that achieved in the continuous‐flow homogeneous catalytic hydrogenation, and a factor of 3–10 more efficient compared to the typical results of heterogeneous continuous‐flow hydrogenations.
Vibronic Spectroscopy of Sympathetically Cooled CaH+
Authors: Rugango René , Calvin Aaron T. , Janardan Smitha , Shu Gang , Brown Kenneth R. 
Published: July 2016

AbstractWe report the measurement of the 11Σ→21Σ transition of CaH+ by resonance‐enhanced photodissociation of CaH+ that is co‐trapped with laser‐cooled Ca+. We observe four resonances that we assign to transitions from the vibrational v=0 ground state to the v′=1–4 excited states based on theoretical predictions. A simple theoretical model that assumes instantaneous dissociation after resonant excitation yields results in good agreement with the observed spectral features except for the unobserved v′=0 peak. This discrepancy is attributed to an insufficient understanding of the dissociation process, and further experimental and theoretical studies are required to confirm the assignment. The resolution of our experiment is limited by the mode‐locked excitation laser, but this survey spectroscopy enables future rotationally resolved studies with applications in astrochemistry and precision measurement.
Ionic Liquid Ordering at an Oxide Surface
Authors: Wagstaffe Michael , Jackman Mark J. , Syres Karen L. , Generalov Alexander , Thomas Andrew G. 
Published: July 2016

AbstractThe interaction of the ionic liquid [C4C1Im][BF4] with anatase TiO2, a model photoanode material, has been studied using a combination of synchrotron radiation photoelectron spectroscopy and near‐edge X‐ray absorption fine structure spectroscopy. The system is of interest as a model for fundamental electrolyte–electrode and dye‐sensitized solar cells. The initial interaction involves degradation of the [BF4]− anion, resulting in incorporation of F into O vacancies in the anatase surface. At low coverages, [C4C1Im][BF4] is found to order at the anatase(101) surface via electrostatic attraction, with the imidazolium ring oriented 32±4° from the anatase TiO2 surface. As the coverage of ionic liquid increases, the influence of the oxide surface on the topmost layers is reduced and the ordering is lost.
Nonparameningeal head and neck rhabdomyosarcoma in children and adolescents: Lessons from the consecutive International Society of Pediatric Oncology Malignant Mesenchymal Tumor studies
Authors: Orbach Daniel , Mosseri Veronique , Gallego Soledad , Kelsey Anna , Devalck Christine , Brenann Bernadette , van Noesel Max M. , Bergeron Christophe , Merks Johannes H. M. , Rechnitzer Catherine , Jenney Meriel , Minard–Colin Veronique , Stevens Michael 
Published: July 2016

AbstractBackgroundThis article reports risk factors and long‐term outcome in localized nonparameningeal head and neck rhabdomyosarcomas in children and adolescents from a combined dataset from 3 consecutive international trials.MethodsData from 140 children (9.3% of total) prospectively enrolled in the International Society of Pediatric Oncology Malignant Mesenchymal Tumor (SIOP‐MMT)‐84/89/95 studies were analyzed.ResultsPrimary site was: superficial face in 46%; oral cavity (21%); neck (19%); and salivary glands (14%). Local control was achieved in 96%, but 49% relapsed (locoregionally 91%). At median follow‐up of 10 years, 5‐year overall survival (OS) was 74.7% (67.4% to 81.9%) and event‐free survival 48.9% (40.6% to 57.2%), although this improved with successive studies. Radiotherapy (RT) as first‐line treatment was independently prognostic for event‐free survival (relative risk [RR] = 0.4 [range, 0.2–0.7]; p < .01) even if it did not impact OS (RR = 1 [range, 0.5–2]).ConclusionHigh rates of locoregional relapse were seen in head and neck rhabdomyosarcoma that should be prevented by more frequent use of RT in this primary. © 2016 Wiley Periodicals, Inc. Head Neck 39: 24–31, 2017
Optimal configuration of respiratory navigator gating for the quantification of left ventricular strain using spiral cine displacement encoding with stimulated echoes (DENSE) MRI
Authors: Hamlet Sean M. , Haggerty Christopher M. , Suever Jonathan D. , Wehner Gregory J. , Andres Kristin N. , Powell David K. , Zhong Xiaodong , Fornwalt Brandon K. 
Published: July 2016

PurposeTo determine the optimal respiratory navigator gating configuration for the quantification of left ventricular strain using spiral cine displacement encoding with stimulated echoes (DENSE) MRI.Materials and MethodsTwo‐dimensional spiral cine DENSE was performed on a 3 Tesla MRI using two single‐navigator configurations (retrospective, prospective) and a combined “dual‐navigator” configuration in 10 healthy adults and 20 healthy children. The adults also underwent breathhold DENSE as a reference standard for comparisons. Peak left ventricular strains, signal‐to‐noise ratio (SNR), and navigator efficiency were compared. Subjects also underwent dual‐navigator gating with and without visual feedback to determine the effect on navigator efficiency.ResultsThere were no differences in circumferential, radial, and longitudinal strains between navigator‐gated and breathhold DENSE (P = 0.09–0.95) (as confidence intervals, retrospective: [‐1.0%–1.1%], [‐7.4%–2.0%], [‐1.0%–1.2%]; prospective: [‐0.6%–2.7%], [‐2.8%–8.3%], [‐0.3%–2.9%]; dual: [‐1.6%–0.5%], [‐8.3%–3.2%], [‐0.8%–1.9%], respectively). The dual configuration maintained SNR compared with breathhold acquisitions (16 versus 18, P = 0.06). SNR for the prospective configuration was lower than for the dual navigator in adults (P = 0.004) and children (P < 0.001). Navigator efficiency was higher (P < 0.001) for both retrospective (54%) and prospective (56%) configurations compared with the dual configuration (35%). Visual feedback improved the dual configuration navigator efficiency to 55% (P < 0.001).ConclusionWhen quantifying left ventricular strains using spiral cine DENSE MRI, a dual navigator configuration results in the highest SNR in adults and children. In adults, a retrospective configuration has good navigator efficiency without a substantial drop in SNR. Prospective gating should be avoided because it has the lowest SNR. Visual feedback represents an effective option to maintain navigator efficiency while using a dual navigator configuration.Level of Evidence: 2J. Magn. Reson. Imaging 2017;45:786–794.
Manifest domains: analysis and description
Authors: Bjørner Dines 
Published: July 2016

Abstract

We show that manifest domains, an understanding of which are a prerequisite for software requirements prescriptions, can be precisely described: narrated and formalised. We show that such manifest domains can be understood as a collection of endurant, that is, basically spatial entities: parts, components and materials, and perdurant, that is, basically temporal entities: actions, events and behaviours. We show that parts can be modeled in terms of external qualities whether: atomic or composite parts, having internal qualities: unique identifications, mereologies, which model relations between parts, and attributes. We show that the manifest domain analysis endeavour can be supported by a calculus of manifest domain analysis prompts: is_entity, is_endurant, is_perdurant, is_part, is_component, is_material, is_atomic, is_composite, has_components, has_materials, has_concrete_type, attribute_names, is_stationary, etcetera; and show how the manifest domain description endeavour can be supported by a calculus of manifest domain description prompts: observe_part_sorts, observe_part_type, observe_components, observe_materials, observe_unique_identifier, observe_mereology, observe_attributes. We show how to model attributes, essentially following Michael Jackson (Software requirements & specifications: a lexicon of practice, principles and prejudices. ACM Press, Addison-Wesley, Reading,
1995
), but with a twist: The attribute model introduces the attribute analysis prompts is_static_attribute, is_dynamic_attribute, is_inert_attribute, is_reactive_attribute, is_active_attribute, is_autonomous_attribute, is_biddable_attribute and is_programmable_attribute. The twist suggests ways of modeling “access” to the values of these kinds of attributes: the static attributes by simply
“copying”
them, once, the reactive and programmable attributes by
“carrying”
them as function parameters whose values are kept always updated, and the remaining, the external_attributes, by inquiring, when needed, as to their value, as if they were always offered on CSP-like channels (Hoare, Communicating sequential processes. C.A.R. Hoare series in computer science. Prentice-Hall International, London,
2004
). We show how to model essential aspects of perdurants in terms of their signatures based on the concepts of endurants. And we show how one can “compile” descriptions of endurant parts into descriptions of perdurant behaviours. We do not show prompt calculi for perdurants. The above contributions express a method with principles, techniques and tools for constructing domain descriptions. It is important to realise that we do not wish to nor claim that the method can describe all that it is interesting to know about domains.
Implementation of a Hospital Electronic Surgical Registry in a Lower‐Middle‐Income Country
Authors: Dasari Mohini , Garbett Marcelo , Miller Elizabeth , Machaín Gustavo M. , Puyana Juan Carlos 
Published: July 2016

AbstractBackgroundWhile the benefits of using electronic health records (EHRs) in both developed and low‐ and middle‐income countries are known, the barriers to implementing EHRs in lower‐middle‐income countries have not been fully characterized. We assessed organizational readiness for implementation of a mobile (tablet‐based) EHR, to create a real‐time electronic surgical registry, in a busy lower‐middle‐income country hospital.
MethodsSix semi‐structured focus groups were conducted with hospital administrators, faculty surgeons, surgical residents, interns, nurses and medical students in a large urban hospital in Asuncion, Paraguay. Focus groups were conducted over the course of three weeks during the pre‐implementation phase to identify barriers to implementation. Focus group data were coded using the Theoretical Domains Framework (TDF), which are 12 validated domains related to behavior change.ResultsReinforcement, environmental context/resources and roles/responsibilities were the most relevant TDF domains that emerged. Residents and students were more uncertain than faculty and department heads about who would enforce the use of the tool in place of paper charting. Internet quality was a concern raised by all. The local, normative hierarchical structure within the surgical department, including piecemeal communication between the department heads and the residents about roles and responsibilities, was a major perceived barrier to implementation.ConclusionsUncertainties about reinforcement, roles and responsibilities for using a novel EHR tool, and technology infrastructure are potential barriers to address in the pre‐implementation phase of introducing an EHR to a lower‐middle‐income country surgical service. Addressing these potential barriers with all stakeholders prior to implementation will be a critical next step in this effort.
Impact of Contraceptive Type on Sexual Desire of Women and of Men Partnered to Contraceptive Users
Authors: Mark Kristen P. , Leistner Christine E. , Garcia Justin R. 
Published: July 2016

ABSTRACT

Introduction
Research investigating the impact of contraceptive use on sexual desire has produced mixed results. This scholarship also has had inconsistent methodology, with some studies not separating contraceptive types and others lacking non-hormonal comparison groups. Relationship context of contraceptive use and sexual behavior also have not been well represented.

Aims
To investigate the impact of contraceptive type on sexual desire in women and in men who are partnered to contraceptive-using women.

Methods
In two separate studies we examined the impact of contraceptives on the sexual desire of women currently using contraceptives and men partnered to women using contraceptives. The first study examined the impact of contraceptive type on sexual desire in women and in men partnered to contraceptive users in relationships of different lengths. The second study examined this impact in heterosexual couples in long-term relationships.

Main Outcome Measures
Solitary and dyadic sexual desire as measured by the Sexual Desire Inventory and contraceptive type as categorized into three types: oral hormonal contraceptive, other hormonal contraceptive, and non-hormonal contraceptive.

Results
Contraceptive type significantly affected solitary and dyadic desire. Women on non-hormonal contraceptives reported higher solitary sexual desire than women on other hormonal contraceptives. Women on oral hormonal contraceptives reported significantly higher dyadic sexual desire than women on non-hormonal contraceptives. In male partners of female contraceptive users, solitary and dyadic sexual desires were not affected by partner contraceptive type. In the multivariate model, relationship length and age were stronger predictors of contraceptive type than was solitary or dyadic sexual desire. At the couple level, contraceptive type also was not related to solitary or dyadic sexual desire in men and women.

Conclusion
Contraceptive type can affect solitary and dyadic sexual desire in women; however, contextual factors seem to be stronger predictors of sexual desire for long-term coupled women and men than contraception type.