bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Influence of the Amide Linkage in the FeIII‐Binding Properties of Catechol‐Modified Rosamine Derivatives
Authors: Queirós Carla , Leite Andreia , G. M. Couto Maria , Cunha‐Silva Luís , Barone Giampaolo , de Castro Baltazar , Rangel Maria , M. N. Silva André , M. G. Silva Ana 
Published: September 2015

AbstractThe two new fluorescent ligands RosCat1 and RosCat2 contain catechol receptors connected to rosamine platforms through an amide linkage and were synthesized by using microwave‐assisted coupling reactions of carboxyl‐ or amine‐substituted rosamines with the corresponding catechol units and subsequent deprotection. RosCat1 possesses a reverse amide, whereas RosCat2 has the usual oriented amide bond (HNCO vs. CONH, respectively). The ligands were characterized by means of NMR spectroscopy, mass‐spectrometry, and DFT calculations and X‐ray crystallography studies for RosCat1. The influence of the amide linkage on the photophysical properties of the fluorescent ligands was assessed in different solvents and showed a higher fluorescence quantum yield for RosCat1. The coordination chemistry of these ligands with a FeIII center has been rationalized by mass‐spectrometric analysis and semiempirical calculations. Octahedral FeIII complexes were obtained by the chelation of three RosCat1 or RosCat2 ligands. Interestingly, the unconventional amide connectivity in RosCat1 imposes the formation of an eight‐membered ring on the chelate complex through a “salicylate‐type” mode of coordination.
Unusual Transformation from a Solvent‐Stabilized 1D Coordination Polymer to a Metal–Organic Framework (MOF)‐Like Cross‐Linked 3D Coordination Polymer
Authors: Lee Seung‐Chul , Choi Eun‐Young , Lee Sang‐Beom , Kim Sang‐Wook , Kwon O‐Pil 
Published: September 2015

AbstractAn unusual 1D‐to‐3D transformation of a coordination polymer based on organic linkers containing highly polar push–pull π‐conjugated side chains is reported. The coordination polymers are synthesized from zinc nitrate and an organic linker, namely, 2,5‐bis{4‐[1‐(4‐nitrophenyl)pyrrolidin‐2‐yl]butoxy}terephthalic acid, which possesses highly polar (4‐nitrophenyl)pyrrolidine groups, with high dipole moments of about 7 D. The coordination polymers exhibit an unusual transformation from a soluble, solvent‐stabilized 1D coordination polymer into an insoluble, metal–organic framework (MOF)‐like 3D coordination polymer. The coordination polymer exhibits good film‐forming ability, and the MOF‐like films are insoluble in conventional organic solvents.
New Insights into the Nature of Co‐components and Their Impact on Pd Structure: X‐ray Absorption Studies on Toluene Acetoxylation Catalysts
Authors: Gatla Suresh , Radnik Jörg , Madaan Neetika , Pohl Marga‐Martina , Mathon Olivier , Rogalev Andrei , Narayana Kalevaru Venkata , Martin Andreas , Pascarelli Sakura , Brückner Angelika 
Published: September 2015

AbstractCo‐components are a powerful tool to tune the performance of catalysts, but their nature and their impact on the catalysts is often controversially discussed. In this study X‐ray absorption spectroscopy (XAS) was employed to elucidate the nature of co‐components and their impact on the catalytic reaction. In anatase‐supported Pd‐based catalysts for the gas‐phase acetoxylation of toluene, less noble co‐components (e.g., Mn, Co, and Sb) spread over the support in their oxidic form and changed their valence state on stream. Incorporated atoms such as C or a small part of the Sb affect the electronic structure of Pd. For the noble Au, only a weak interaction with the support and Pd was observed during time on stream. Only XAS at the K‐edges together with investigations of the Pd L‐edge for a better understanding of the electronic structure, supplemented by STEM for elemental mapping, allow such detailed insights.
Regio‐ and Diastereoselective and Enantiospecific Metal‐Free C(sp3)H Arylation: Facile Access to Optically Active 5‐Aryl 2,5‐Disubstituted Pyrrolidines
Authors: Haldar Surajit , Roy Subhra Kanti , Maity Bholanath , Koley Debasis , Jana Chandan K. 
Published: September 2015

AbstractOptically active 5‐aryl 2,5‐disubstituted pyrrolidines are the principal structural moiety of many bioactive compounds including natural products and catalysts for asymmetric synthesis. A highly regio‐ and diastereoselective and enantiospecific method for direct CH arylation of aliphatic amine has been developed. Structurally diverse enantiopure arylated pyrrolidines were synthesized from commercially available starting materials, through a single‐step three‐component reaction under metal‐ and oxidant‐free conditions. Furthermore, the complex analogous structure of CCK antagonist RP 66803 and angiotensin‐converting enzyme inhibitors was easily constructed using the synthesized arylated pyrrolidine derivative. Detailed theoretical calculations (M06‐2X/TZVPP/SMD//M06‐2X/6‐31+G(d,p) level) were also carried to investigate the mechanism and high level of stereocontrol involved in this direct sp3 CH arylation reaction. Preference for a given regio‐ and stereoselectivity in the arylated product can be explained through elucidation of the mechanism for dehydration, generating azomethine ylide, and for the final re‐aromatization step. The calculated energies reveals that the re‐aromatization step is essentially rate determining, accompanying an activation barrier of Δ≠=25.6 kcal mol−1.
On the Critical Effect of the Metal (Mo vs. W) on the [3+2] Cycloaddition Reaction of M3S4 Clusters with Alkynes: Insights from Experiment and Theory
Authors: Bustelo Emilio , Gushchin Artem L. , Fernández‐Trujillo M. Jesús , Basallote Manuel G. , Algarra Andrés G. 
Published: September 2015

AbstractWhereas the cluster [Mo3S4(acac)3(py)3]+ ([1]+, acac=acetylacetonate, py=pyridine) reacts with a variety of alkynes, the cluster [W3S4(acac)3(py)3]+ ([2]+) remains unaffected under the same conditions. The reactions of cluster [1]+ show polyphasic kinetics, and in all cases clusters bearing a bridging dithiolene moiety are formed in the first step through the concerted [3+2] cycloaddition between the CC atoms of the alkyne and a Mo(μ‐S)2 moiety of the cluster. A computational study has been conducted to analyze the effect of the metal on these concerted [3+2] cycloaddition reactions. The calculations suggest that the reactions of cluster [2]+ with alkynes feature ΔG≠ values only slightly larger than its molybdenum analogue, however, the differences in the reaction free energies between both metal clusters and the same alkyne reach up to approximately 10 kcal mol−1, therefore indicating that the differences in the reactivity are essentially thermodynamic. The activation strain model (ASM) has been used to get more insights into the critical effect of the metal center in these cycloadditions, and the results reveal that the change in reactivity is entirely explained on the basis of the differences in the interaction energies Eint between the cluster and the alkyne. Further decomposition of the Eint values through the localized molecular orbital‐energy decomposition analysis (LMO‐EDA) indicates that substitution of the Mo atoms in cluster [1]+ by W induces changes in the electronic structure of the cluster that result in weaker intra‐ and inter‐fragment orbital interactions.
Cobalt(III) Chaperone Complexes of Curcumin: Photoreduction, Cellular Accumulation and Light‐Selective Toxicity towards Tumour Cells
Authors: Renfrew Anna K. , Bryce Nicole S. , Hambley Trevor 
Published: September 2015

AbstractLight‐activated prodrugs offer the potential for highly selective tumour targeting. However, the application of many photoactivated chemotherapeutics is limited by a requirement for oxygen, or for short activation wavelengths that can damage surrounding tissue. Herein, we present a series of cobalt(III)‐curcumin prodrugs that can be activated by visible light under both oxygenated and hypoxic conditions. Furthermore, the photoproduct can be controlled by the activation wavelength: green light yields free curcumin, whereas blue light induces photolysis of curcumin to a phototoxic product. Confocal fluorescence microscopy and phototocytotoxicity studies in DLD‐1 and MCF‐7 tumour cells demonstrated that the cobalt(III) prodrugs are nontoxic in the dark but accumulate in significant concentrations in the cell membrane. When cells were treated with light for 15  min, the cytotoxicity of the cobalt complexes increased by up to 20‐fold, whereas free curcumin exhibited only a two‐fold increase in cytotoxicity. The nature of the ancillary ligand and cobalt reduction potential were found to strongly influence the stability and biological activity of the series.
Cycle Factors and Renewal Theory
Authors: Kahn Jeff , Lubetzky Eyal , Wormald Nicholas 
Published: September 2015

For which values of k does a uniformly chosen 3‐regular graph G on n vertices typically contain n/k vertex‐disjoint k‐cycles (a k‐cycle factor)? To date, this has been answered for k = n and for k ≪  log n; the former, the Hamiltonicity problem, was finally answered in the affirmative by Robinson and Wormald in 1992, while the answer in the latter case is negative since with high probability (w.h.p.) most vertices do not lie on k‐cycles.A major role in our study of this problem is played by renewal processes without replacement, where one wishes to estimate the probability that in a uniform permutation of a given set of positive integers, the partial sums hit a designated target integer. Using sharp tail estimates for these renewal processes, which may be of independent interest, we settle the cycle factor problem completely: the “threshold” for a k‐cycle factor in G as above is κ0 log2 n with . To be precise, G contains a k‐cycle factor w.h.p. if

urn:x-wiley:00103640:media:cpa21613:cpa21613-math-0002

and w.h.p. does not contain one if . Thus, for most values of n the threshold concentrates on the single integer K0(n). As a byproduct, we confirm the “comb conjecture,” an old problem concerning the embedding of certain spanning trees in the random graph (n,p).© 2015 Wiley Periodicals, Inc.
Safety, pharmacokinetics, and pharmacodynamics of PD 0348292, an oral, direct factor Xa inhibitor, after single and multiple dosings in healthy subjects
Authors: Xuan Dawei , McBride Scott , Wastall Philip , Porcari Anthony , DiCarlo Lorenzo , Boyd Rebecca A. 
Published: September 2015

AbstractObjective: The objective of this study was to evaluate PD 0348292 safety, pharmacokinetics, and pharmacodynamics in healthy subjects.Methods: Three phase 1 studies were conducted. Studies 1001 and 1021 were single ascending‐dose studies in healthy subjects randomized to oral PD 0348292 (2.5–150 and 0.1–2.5 mg, respectively) or placebo. Study 1003 was a multiple ascending‐dose study in which 3 cohorts of young subjects received multiple doses of PD 0348292 (5–30 mg) every 12 hours or placebo, and 1 cohort of elderly subjects received a single dose (5 mg) of PD 0348292 or placebo. Drug plasma concentrations were measured. The effects of PD 0348292 on thrombin generation and typical coagulation measures such as prothrombin time, and international normalized ratio were evaluated.Results: Single doses of PD 0348292 were well tolerated. Minor bleeding‐related adverse events were observed following multiple doses of PD 0348292. PD 0348292 exposure increased less than proportionally at doses > 20 mg. Median peak concentrations occurred 3 to 4 hours following administration, and the mean terminal t1/2 value was approximately 10 hours. PD 0348292 demonstrated robust and concentration‐dependent inhibition of thrombin generation, and modest and dose‐related increases in typical coagulation measures.Conclusions: The safety, pharmacokinetics, and pharmacodynamics of PD 0348292 were acceptable for future clinical development.
Charge Localization in the Lithium Iron Phosphate Li3Fe2(PO4)3 at High Voltages in Lithium‐Ion Batteries
Authors: Younesi Reza , Christiansen Ane , Loftager Simon , García‐Lastra Juan Maria , Vegge Tejs , Norby Poul , Holtappels Peter 
Published: September 2015

AbstractPossible changes in the oxidation state of the oxygen ion in the lithium iron phosphate Li3Fe2(PO4)3 at high voltages in lithium‐ion (Li‐ion) batteries are studied using experimental and computational analysis. Results obtained from synchrotron‐based hard X‐ray photoelectron spectroscopy and density functional theory (DFT) show that the oxidation state of O2− ions is altered to higher oxidation states (Oδ−, δ<2) upon charging Li3Fe2(PO4)3 to 4.7 V.
Seven‐Coordinate Luminophores: Brilliant Luminescence of Lanthanide Complexes with C3v Geometrical Structures
Authors: Yanagisawa Kei , Nakanishi Takayuki , Kitagawa Yuichi , Seki Tomohiro , Akama Tomoko , Kobayashi Masato , Taketsugu Tetsuya , Ito Hajime , Fushimi Koji , Hasegawa Yasuchika 
Published: September 2015

AbstractEnhanced luminescence properties of mononuclear lanthanide complexes with asymmetric seven‐coordination structures are reported for the first time. The lanthanide complexes are composed of a lanthanide ion (EuIII or TbIII), three tetramethyl heptanedionato ligands, and one triphenylphosphine oxide ligand. The coordination geometries of the lanthanide complexes have been evaluated by using single‐crystal X‐ray analyses and shape‐measurement calculations. The complexes are categorized to be seven‐coordinate monocapped octahedral structures (point group C3v). The seven‐coordinate lanthanide complexes show high intrinsic emission quantum yields, extra‐large radiative rate constants, and unexpected small nonradiative rate constants. The brilliant luminescence properties have been elucidated in terms of the asymmetric coordination geometry and small vibrational quanta related to thermal relaxation.
Carbon pools in stream‐riparian corridors: legacy of disturbance along mountain streams of south‐eastern Wyoming
Authors: Ruffing Claire M. , Dwire Kathleen A. , Daniels Melinda D. 
Published: September 2015

AbstractStreams and their accompanying riparian environments are intrinsic components of terrestrial carbon cycling. However, they have been understudied in terms of the magnitude of their storage components and the role of disturbance in determining carbon storage capacity. This study presents partial carbon budgets for stream‐riparian corridors along six study reaches in mountain headwater streams of southeast Wyoming to evaluate the impact of tie‐driving, a historic disturbance legacy, on contemporary carbon storage. Detailed measurements of biomass were collected for in‐stream components of carbon including fine and coarse particulate organic matter and in‐stream large wood. Biomass was also estimated for riparian components including standing trees (live and dead), regenerating conifers, shrubs and herbaceous vegetation, downed wood, litter, and duff (partially decayed litter). Biomass was converted to carbon for all components and differences in storage were compared between tie‐driven and non‐driven reaches. Carbon content in riparian soils (to approximately 20 cm) was also measured. Twice the amount of carbon was stored in the riparian areas relative to the streams; most carbon was stored in standing trees (live and dead). While overall carbon storage within the riparian areas and streams were similar between disturbance conditions, the amount of carbon stored in large in‐stream wood and downed wood on the floodplain was significantly higher in systems that were not tie‐driven. The results of this study indicate that legacies of tie‐driving influence carbon storage within the region, while also capturing baseline estimates of carbon storage in the wake of recent bark beetle infestations. Copyright © 2015 John Wiley & Sons, Ltd.
The extreme 2013/2014 winter storms: hydrodynamic forcing and coastal response along the southwest coast of England
Authors: Masselink Gerd , Scott Tim , Poate Tim , Russell Paul , Davidson Mark , Conley Daniel 
Published: September 2015

AbstractThe southwest coast of England was subjected to an unusually energetic sequence of Atlantic storms during the 2013/2014 winter, with the 8‐week period from mid‐December to mid‐February representing the most energetic period since at least 1953. A regional analysis of the hydrodynamic forcing and morphological response of these storms along the SW coast of England highlighted the importance of both storm‐ and site‐specific conditions.The key factor that controls the Atlantic storm wave conditions along the south coast of southwest England is the storm track. Energetic inshore wave conditions along this coast require a relatively southward storm track which enables offshore waves to propagate up the English Channel relatively unimpeded. The timing of the storm in relation to the tidal stage is also important, and coastal impacts along the macro‐tidal southwest coast of England are maximised when the peak storm waves coincide with spring high tide. The role of storm surge is limited and rarely exceeds 1 m.The geomorphic storm response along the southwest coast of England displayed considerable spatial variability; this is mainly attributed to the embayed nature of the coastline and the associated variability in coastal orientation. On west‐facing beaches typical of the north coast, the westerly Atlantic storm waves approached the coastline shore‐parallel, and the prevailing storm response was offshore sediment transport. Many of these north coast beaches experienced extensive beach and dune erosion, and some of the beaches were completely stripped of sediment, exposing a rocky shore platform. On the south coast, the westerly Atlantic storm waves refract and diffract to become southerly inshore storm waves and for the southeast‐facing beaches this results in large incident wave angles and strong eastward littoral drift. Many south coast beaches exhibited rotation, with the western part of the beaches eroding and the eastern part accreting. © 2015 The Authors.Earth Surface Processes and Landformspublished by John Wiley & Sons Ltd.
Preparation and stability of W/O/W emulsions containing sucrose as weighting agent
Authors: Zhang Jian , Reineccius Gary A. 
Published: September 2015

AbstractThe objective of present study was to evaluate the use of sucrose as a weighting agent in W/O/W emulsions. Placing sucrose in the internal water phase could increase the density of the oil droplet and provide natural weighing to the oil phase. A 60 wt% sucrose solution with or without gelatin served as inner aqueous phase (W). Orange oil terpenes (OT) or Miglyol 812 (MCT) were compared as oil phase (O). Different concentrations of polyglycerol polyricinoleate (PGPR) were evaluated as lipophilic emulsifier. Gum Arabic (GA), modified starch (MS), and/or Tween 20 were evaluated as hydrophilic emulsifiers. Mean droplet diameter (MDD) and encapsulation efficiency (EE) were measured with yellow #6 as a marker incorporated in inner aqueous phase. Nano‐sized W/O emulsions were formed with MDD as small as of 72 nm by using Microfluidization. Gelling the inner phase significantly increased droplet size of W/O emulsions. GA‐stabilized W/O/W emulsions showed highest dye retention (EE > 85%) and smallest MDD (0.75 to 4.5 µm), whereas MS and Tween 20 showed poor performance (EE <50%). Both concentrated and diluted W/O/W emulsions with MCT as oil phase stabilized by GA showed good stability in MDD, EE and turbidity during four weeks of storage at 23 °C. The results demonstrated the potential and challenges of creating stable beverage cloud applications based on W/O/W emulsions using sucrose as a natural weighting agent. Copyright © 2015 John Wiley & Sons, Ltd.
Brain volumetric changes and cognitive ageing during the eighth decade of life
Authors: Ritchie Stuart J. , Dickie David Alexander , Cox Simon R. , Valdes Hernandez Maria del C. , Corley Janie , Royle Natalie A. , Pattie Alison , Aribisala Benjamin S. , Redmond Paul , Muñoz Maniega Susana , Taylor Adele M. , Sibbett Ruth , Gow Alan J. , Starr John M. , Bastin Mark E. , Wardlaw Joanna M. , Deary Ian J. 
Published: September 2015

AbstractLater‐life changes in brain tissue volumes—decreases in the volume of healthy grey and white matter and increases in the volume of white matter hyperintensities (WMH)—are strong candidates to explain some of the variation in ageing‐related cognitive decline. We assessed fluid intelligence, memory, processing speed, and brain volumes (from structural MRI) at mean age 73 years, and at mean age 76 in a narrow‐age sample of older individuals (n = 657 with brain volumetric data at the initial wave, n = 465 at follow‐up). We used latent variable modeling to extract error‐free cognitive levels and slopes. Initial levels of cognitive ability were predictive of subsequent brain tissue volume changes. Initial brain volumes were not predictive of subsequent cognitive changes. Brain volume changes, especially increases in WMH, were associated with declines in each of the cognitive abilities. All statistically significant results were modest in size (absolute r‐values ranged from 0.114 to 0.334). These results build a comprehensive picture of macrostructural brain volume changes and declines in important cognitive faculties during the eighth decade of life. Hum Brain Mapp 36:4910–4925, 2015. © 2015 The Authors. Human Brain Mapping Published by Wiley Periodicals, Inc
Transition Metal‐Free One‐Pot Protocol Toward Conjugated Arylbutadiynyl Sulfides
Authors: Zhang Yanqin , Xiao Jing , Dong Wanrong , Peng Zhihong , An Delie 
Published: September 2015

ABSTRACTAn efficient strategy toward conjugated arylbuta‐1,3‐diynyl sulfides (Ar–C≡C–C≡C–SR) was herein reported. In the newly developed one‐pot, three‐steps protocol, the synthetically or materially significant arylbuta‐1,3‐diynyl sulfides were obtained from easily accessible 4‐hydrocarbylthio‐1‐arylbuta‐1,3‐diones, avoiding usage of expensive terminal aryl acetylenes as substrates or any transition metal complexes as catalysts. The gram‐scale experiment of the efficient methodology with acceptable yield afforded a good alternative of industrial interest.
Strategies and long‐term outcomes in the surgical management of tympanojugular paragangliomas
Authors: Prasad Sampath Chandra , Mimoune Hassen Ait , Khardaly Mohsen , Piazza Paolo , Russo Alessandra , Sanna Mario 
Published: September 2015

AbstractBackgroundThe purpose of this study was to share our review of surgical strategies and long‐term outcomes in the management of tympanojugular paragangliomas.MethodsThis was a retrospective study with a literature review. The records of 184 patients with 185 tympanojugular paragangliomas were analyzed for tumor class, surgical procedure, preoperative vascular management, and perioperative sequelae.ResultsOf class C1, C2, C3, and C4 tumors, we found 46 (24.9%), 95 (51.3%), 41 (22.2%), and 3 (1.6%), respectively. One hundred four (56.2%) tumors had intracranial extensions and 8 (4.3%) involved the vertebral artery. A single‐stage procedure was adopted in 158 (85.4%) tumors. The infratemporal fossa type A approach was used in all cases. In 17 patients (9.7%), an intra‐arterial stenting of the internal carotid artery was performed. Gross‐total tumor removal was achieved in 166 cases (89.7%) and 4 (2.4%) among them developed a recurrence.ConclusionA thorough understanding of skull base techniques and a logical decision‐making process in the management of tympanojugular paragangliomas can achieve a high rate of success in terms of recurrences and complications. © 2015 Wiley Periodicals, Inc. Head Neck 38: 871–885, 2016