bluuebunny/crossref_metadata_2025 huggingface dataset:
A generalized equilibrium model for predicting daily to interannual shoreline response
Authors: Splinter Kristen D. , Turner Ian L. , Davidson Mark A. , Barnard Patrick , Castelle Bruno , Oltman‐Shay Joan
Published: August 2014

Coastal zone management requires the ability to predict coastline response to storms and longer‐term seasonal to interannual variability in regional wave climate. Shoreline models typically rely on extensive historical observations to derive site‐specific calibration. To circumvent the challenge that suitable data sets are rarely available, this contribution utilizes twelve 5+ year shoreline data sets from around the world to develop a generalized model for shoreline response. The shared dependency of model coefficients on local wave and sediment characteristics is investigated, enabling the model to be recast in terms of these more readily measurable quantities. Study sites range from microtidal to macrotidal coastlines, spanning moderate‐ to high‐energy beaches. The equilibrium model adopted here includes time varying terms describing both the magnitude and direction of shoreline response as a result of onshore/offshore sediment transport between the surf zone and the beach face. The model contains two coefficients linked to wave‐driven processes: (1) the response factor (φ) that describes the “memory” of a beach to antecedent conditions and (2) the rate parameter (c) that describes the efficiency with which sand is transported between the beach face and surf zone. Across all study sites these coefficients are shown to depend in a predictable manner on the dimensionless fall velocity (Ω), that in turn is a simple function of local wave conditions and sediment grain size. When tested on an unseen data set, the new equilibrium model with generalized forms ofφandcexhibited high skill (Brier Skills Score, BSS = 0.85).
Morphology and controls on the position of a gravel‐sand transition: Fraser River, British Columbia
Authors: Venditti Jeremy G. , Church Michael
Published: August 2014

Alluvial river channels often exhibit a relatively abrupt transition from gravel‐ to sand‐bedded conditions. The phenomenon is well documented, but few prior studies have analyzed the spatial variability through reaches where transitions occur. The downstream fining pattern observed in the Fraser River is cited as a classic example of an abrupt gravel‐sand transition in a large alluvial channel. However, important questions regarding the exact location of the transition, its sedimentology and morphology, and what controls its location remain unanswered. Here we present observations of the downstream change in bed material grain size, river bed topography, and channel hydraulics through the reach within which the transition occurs. These observations indicate that the gravel‐sand transition is characterized by a terminating gravel wedge, but there are patches of gravel downstream of the wedge forming a diffuse extension. We show that there is a dramatic decrease in shear stress at the downstream end of the wedge and a consequent cessation of general gravel mobility. We argue that the patches of gravel observed beyond the wedge are the result of enhanced mobility of fine gravel over a sand bed. We also find that sand in suspension declines rapidly at the downstream end of the wedge, suggesting that sand is delivered to the bed, completing the sedimentary conditions for a gravel‐sand transition. We propose that the break in river slope associated with the transition is a consequential feature of the transition.
Impacts of forest harvest on cold season land surface conditions and land‐atmosphere interactions in northern Great Lakes states
Authors: Garcia Matthew , Özdogan Mutlu , Townsend Philip A.
Published: August 2014

Land cover change, including temporary disturbances such as forest harvests, can significantly affect established regimes of surface energy balance and moisture exchange, altering flux processes that drive weather and climate. We examined the impacts of forest harvest on winter land‐atmosphere interactions in a temperate region using high‐resolution numerical modeling methods in paired simulations. Using the WRF‐ARW atmospheric model and the Noah land surface model, we simulated the balance of surface sensible and latent heat fluxes and the development and dissipation of a stable nocturnal boundary layer during generally calm synoptic conditions. Our results show reduced daily‐average snow‐covered land surface sensible heat flux (by 80%) and latent heat flux (by 60%) to the atmosphere in forest clearings due to albedo effects and rebalancing of the surface energy budget. We found a land surface cooling effect (−8 W m−2) in snow‐covered cleared areas, consistent with prior modeling studies and conceptual understanding of the mechanisms for midlatitude deforestation to offset anthropogenic global warming at local scales. Results also demonstrate impacts of forest clearing on the passage of a weak cold front due to altered near‐surface winds and boundary layer stability. We show significant differences in both surface conditions and fluxes between harvested and undisturbed forest areas. Our results demonstrate the potential utility of high‐resolution remote sensing analyses to represent transient land cover changes in model simulations of weather and climate, which are usually undertaken at coarser resolutions and often overlook these changes at the land surface.
Effects of transionospheric signal decorrelation on Global Navigation Satellite Systems (GNSS) performance studied from irregularity dynamics around the northern crest of the EIA
Authors: Das T. , Roy B. , Paul A.
Published: August 2014

Transionospheric satellite navigation links operate primarily at L band and are frequently subject to severe degradation of performances arising out of ionospheric irregularities. Various characteristic features of equatorial ionospheric irregularity bubbles like the drift velocity, characteristic velocity, decorrelation time, and decorrelation distance can be determined using spaced aerial measurements at VHF. These parameters measured at VHF from a station Calcutta situated near the northern crest of the Equatorial Ionization Anomaly (EIA) in the geophysically sensitive Indian longitude sector have been correlated with L band scintillation indices and GPS position accuracy parameters for identifying possible proxies to L band scintillations. Good correspondences have been observed between decorrelation times and distances at VHF with GPS S4 and Position Dilution of Precision during periods of GPS scintillations (S4 > 0.3) for February–April 2011, August–October 2011, and February–April 2012. A functional relation has been developed between irregularity drift velocity measured at VHF and S4 at L band during February–April 2011, and validation of measured S4 and predicted values performed during August–October 2011 and February–April 2012. Significant improvement in L band scintillation prediction and consequent navigational accuracy will result using such relations derived from VHF irregularity measurements which are much simpler and inexpensive.
Bortezomib‐ and thalidomide‐induced peripheral neuropathy in multiple myeloma: clinical and molecular analyses of a phase 3 study
Authors: Tacchetti Paola , Terragna Carolina , Galli Monica , Zamagni Elena , Petrucci Maria Teresa , Pezzi Annalisa , Montefusco Vittorio , Martello Marina , Tosi Patrizia , Baldini Luca , Peccatori Jacopo , Ruggieri Miriana , Pantani Lucia , Lazzaro Antonio , Elice Francesca , Rocchi Serena , Gozzetti Alessandro , Cavaletti Guido , Palumbo Antonio , Cavo Michele
Published: August 2014

A subanalysis of the GIMEMA‐MMY‐3006 trial was performed to characterize treatment‐emergent peripheral neuropathy (PN) in patients randomized to thalidomide‐dexamethasone (TD) or bortezomib‐TD (VTD) before and after double autologous transplantation (ASCT) for multiple myeloma (MM). A total of 236 patients randomized to VTD and 238 to TD were stratified according to the emergence of grade ≥2 PN. Gene expression profiles (GEP) of CD138+ plasma cells were analyzed in 120 VTD‐treated patients. The incidence of grade ≥2 PN was 35% in the VTD arm and 10% in the TD arm (P < 0.001). PN resolved in 88 and 95% of patients in VTD and TD groups, respectively. Rates of complete/near complete response, progression‐free and overall survival were not adversely affected by emergence of grade ≥2 PN. Baseline characteristics were not risk factors for PN, while GEP analysis revealed the deregulated expression of genes implicated in cytoskeleton rearrangement, neurogenesis, and axonal guidance. In conclusion, in comparison with TD, incorporation of VTD into ASCT was associated with a higher incidence of PN which, however, was reversible in most of the patients and did not adversely affect their outcomes nor their ability to subsequently receive ASCT. GEP analysis suggests an interaction between myeloma genetic profiles and development of VTD‐induced PN. Am. J. Hematol. 89:1085–1091, 2014. © 2014 Wiley Periodicals, Inc.
Cancer mortality among Brazilian dentists
Authors: Koifman Sergio , Malhão Thainá Alves , Pinto de Oliveira Gisele , de Magalhães Câmara Volney , Koifman Rosalina Jorge , Meyer Armando
Published: August 2014

Background

Previous studies have variably shown excess risks of elected cancers among dentists.

Methods

National Brazilian mortality data were used to obtain mortality patterns among dentists between 1996 and 2004. Cancer mortality odds ratios (MORs) and cancer proportional mortality ratios for all cancer sites were calculated, using the general population and physicians and lawyers as comparison groups.

Results

Female dentists from both age strata showed higher risks for breast, colon‐rectum, lung, brain, and non‐Hodgkin lymphoma. Compared to physicians and lawyers, higher MOR estimates were observed for brain cancer among female dentists 20–49 yr. Among male dentists, higher cancer mortality was found for colon‐rectum, pancreas, lung, melanoma, and non‐Hodgkin lymphoma. Higher risk estimates for liver, prostate, bladder, brain, multiple myeloma and leukemia were observed among 50–79 yr old male dentists.

Discussion

If confirmed, these results indicate the need for limiting occupational exposures among dentists in addition to establishing screening programs to achieve early detection of selected malignant tumors. Am. J. Ind. Med. 57:1255–1264, 2014. © 2014 Wiley Periodicals, Inc.
Epigenetic therapy for Friedreich ataxia
Authors: Soragni Elisabetta , Miao Wenyan , Iudicello Marco , Jacoby David , De Mercanti Stefania , Clerico Marinella , Longo Filomena , Piga Antonio , Ku Sherman , Campau Erica , Du Jintang , Penalver Pablo , Rai Myriam , Madara Joseph C. , Nazor Kristopher , O'Connor Melinda , Maximov Anton , Loring Jeanne F. , Pandolfo Massimo , Durelli Luca , Gottesfeld Joel M. , Rusche James R.
Published: August 2014

Objective

To investigate whether a histone deacetylase inhibitor (HDACi) would be effective in an in vitro model for the neurodegenerative disease Friedreich ataxia (FRDA) and to evaluate safety and surrogate markers of efficacy in a phase I clinical trial in patients.

Methods

We used a human FRDA neuronal cell model, derived from patient induced pluripotent stem cells, to determine the efficacy of a 2‐aminobenzamide HDACi (109) as a modulator of FXN gene expression and chromatin histone modifications. FRDA patients were dosed in 4 cohorts, ranging from 30mg/day to 240mg/day of the formulated drug product of HDACi 109, RG2833. Patients were monitored for adverse effects as well as for increases in FXN mRNA, frataxin protein, and chromatin modification in blood cells.

Results

In the neuronal cell model, HDACi 109/RG2833 increases FXN mRNA levels and frataxin protein, with concomitant changes in the epigenetic state of the gene. Chromatin signatures indicate that histone H3 lysine 9 is a key residue for gene silencing through methylation and reactivation through acetylation, mediated by the HDACi. Drug treatment in FRDA patients demonstrated increased FXN mRNA and H3 lysine 9 acetylation in peripheral blood mononuclear cells. No safety issues were encountered.

Interpretation

Drug exposure inducing epigenetic changes in neurons in vitro is comparable to the exposure required in patients to see epigenetic changes in circulating lymphoid cells and increases in gene expression. These findings provide a proof of concept for the development of an epigenetic therapy for this fatal neurological disease. Ann Neurol 2014;76:489–508
Kombinierte Rhodium‐ und Photoredoxkatalyse in der C‐H‐Funktionalisierung von Arenen: oxidative Heck‐Reaktionen mit sichtbarem Licht
Authors: Fabry David C. , Zoller Jochen , Raja Sadiya , Rueping Magnus
Published: August 2014

Direkte oxidative metallkatalysierte C‐H‐Funktionalisierungen von Arenen haben sich in den letzten Jahren zu einem wichtigen Gebiet der organischen Synthesechemie entwickelt. Häufig werden in diesen Reaktionen (über)stöchiometrische Mengen an organischen oder anorganischen Oxidantien verwendet. Die Kombination von Rhodiumkatalyse und Photoredoxkatalyse mit sichtbarem Licht ermöglichte nun die direkte katalytische C‐H‐Olefinierung von Arenen. Geringe Mengen (1 Mol‐%) des Photoredoxkatalysators und milde Reaktionsbedingungen erlauben eine effiziente C‐H‐Funktionalisierung mit guter Substratbreite.
A Biomimetic Synthesis of (±)‐Basiliolide B
Authors: Min Long , Zhang Yang , Liang Xuefeng , Huang Junrong , Bao Wenli , Lee Chi‐Sing
Published: August 2014

A highly diastereoselective and practical biomimetic total synthesis of (±)‐basiliolide B has been achieved through the study of the two proposed biosynthetic pathways (O‐methylation and O‐acylation) for the unprecedented 7‐methoxy‐4,5‐dihydro‐3H‐oxepin‐2‐one (C ring). The synthesis featured a cyclopropanation/ring opening strategy for establishing the stereogenic centers at C8 and C9, a biomimetic 2‐pyrone Diels–Alder cycloaddition for the synthesis of the ABD ring system, and finally a highly efficient biomimetic intramolecular O‐acylation for the C ring formation. This result provides an important perspective on the biosynthetic origin of the unprecedented 7‐membered acyl ketene acetal moiety of the C ring.
Sustainable Electrical Energy Storage through the Ferrocene/Ferrocenium Redox Reaction in Aprotic Electrolyte
Authors: Zhao Yu , Ding Yu , Song Jie , Li Gang , Dong Guangbin , Goodenough John B. , Yu Guihua
Published: August 2014

The large‐scale, cost‐effective storage of electrical energy obtained from the growing deployment of wind and solar power is critically needed for the integration into the grid of these renewable energy sources. Rechargeable batteries having a redox‐flow cathode represent a viable solution for either a Li‐ion or a Na‐ion battery provided a suitable low‐cost redox molecule soluble in an aprotic electrolyte can be identified that is stable for repeated cycling and does not cross the separator membrane to the anode. Here we demonstrate an environmentally friendly, low‐cost ferrocene/ferrocenium molecular redox couple that shows about 95 % energy efficiency and about 90 % capacity retention after 250 full charge/discharge cycles.
An Unusual Dehydratase Acting on Glycerate and a Ketoreducatse Stereoselectively Reducing α‐Ketone in Polyketide Starter Unit Biosynthesis
Authors: He Hai‐Yan , Yuan Hua , Tang Man‐Cheng , Tang Gong‐Li
Published: August 2014

Polyketide synthases (PKSs) usually employ a ketoreductase (KR) to catalyze the reduction of a β‐keto group, followed by a dehydratase (DH) that drives the dehydration to form a double bond between the α‐ and β‐carbon atoms. Herein, a DH*‐KR* involved in FR901464 biosynthesis was characterized: DH* acts on glyceryl‐S‐acyl carrier protein (ACP) to yield ACP‐linked pyruvate; subsequently KR* reduces α‐ketone that yields L‐lactyl‐S‐ACP as starter unit for polyketide biosynthesis. Genetic and biochemical evidence was found to support a similar pathway that is involved in the biosynthesis of lankacidins. These results not only identified new PKS domains acting on different substrates, but also provided additional options for engineering the PKS starter pathway or biocatalysis.
Trans‐Selective Radical Silylzincation of Ynamides
Authors: Romain Elise , Fopp Carolin , Chemla Fabrice , Ferreira Franck , Jackowski Olivier , Oestreich Martin , Perez‐Luna Alejandro
Published: August 2014

The silylzincation of terminal ynamides is achieved through a radical‐chain process involving (Me3Si)3SiH and R2Zn. A potentially competing polar mechanism is excluded on the basis of diagnostic control experiments. The unique feature of this addition across the CC bond is its trans selectivity. One‐pot electrophilic substitution of the CZn bond by CuI‐mediated CC bond formation and subsequent manipulation of the CSi bond provides a modular access to Z‐α,β‐disubstituted enamides.
An Unusual Ring‐Contraction/Rearrangement Sequence for Making Functionalized Di‐ and Triquinanes
Authors: Nagaraju Chinta , Prasad Kavirayani R.
Published: August 2014

A novel ring contraction/rearrangement sequence leading to functionalized 2,8‐oxymethano‐bridged di‐ and triquinane compounds is observed in the reaction of various substituted 1‐methyl‐4‐isopropenyl‐6‐oxabicylo[3.2.1]octan‐8‐ones with Lewis acids. The reaction is novel and is unprecedented for the synthesis of di‐ and triquinane frameworks.
Combining Rhodium and Photoredox Catalysis for CH Functionalizations of Arenes: Oxidative Heck Reactions with Visible Light
Authors: Fabry David C. , Zoller Jochen , Raja Sadiya , Rueping Magnus
Published: August 2014

Direct, oxidative metal‐catalyzed CH functionalizations of arenes are important in synthetic organic chemistry. Often, (over‐)stoichoimetric amounts of organic or inorganic oxidants have to be used in these reactions. The combination of rhodium and photoredox catalysis with visible light allows the direct CH olefination of arenes. Small amounts (1 mol %) of a photoredox catalyst resulted in the efficient CH functionalization of a broad range of substrates under mild conditions.
A “Schizophotonic” All‐In‐One Nanoparticle Coating for Multiplexed SE(R)RS Biomedical Imaging
Authors: Iacono Pasquale , Karabeber Hazem , Kircher Moritz F.
Published: August 2014

SERS nanoprobes for in vivo biomedical applications require high quantum yield, long circulation times, and maximum colloidal stability. Traditional synthetic routes require high metal–dye affinities and are challenged by unfavorable electrostatic interactions and limited scalability. We report the synthesis of a new near‐IR active poly(N‐(2‐hydroxypropyl) methacrylamide) (pHPMA). The integration of various SERS reporters into a biocompatible polymeric surface coating allows for controlled dye incorporation, high colloidal stability, and optimized in vivo circulation times. This technique allows the synthesis of very small (<20 nm) SERS probes, which is crucial for the design of excretable and thus highly translatable imaging agents. Depending on their size, the “schizophotonic” nanoparticles can emit both SERS and fluorescence. We demonstrate the capability of this all‐in‐one gold surface coating and SERS reporter for multiplexed lymph‐node imaging.
Switchable Charge‐Transfer in the Photoelectrochemical Energy‐Conversion Process of Ferroelectric BiFeO3 Photoelectrodes
Authors: Cao Dawei , Wang Zhijie , Nasori  , Wen Liaoyong , Mi Yan , Lei Yong
Published: August 2014

Instead of conventional semiconductor photoelectrodes, herein, we focus on BiFeO3 ferroelectric photoelectrodes to break the limits imposed by common semiconductors. As a result of their prominent ferroelectric properties, the photoelectrodes are able to tune the transfer of photo‐excited charges generated either in BiFeO3 or the surface modifiers by manipulating the poling conditions of the ferroelectric domains. At 0 V vs Ag/AgCl, the photocurrent could be switched from 0 μA cm−2 to 10 μA cm−2 and the open‐circuit potential changes from 33 mV to 440 mV, when the poling bias of pretreatment is manipulated from −8 V to +8 V. Additionally, the pronounced photocurrent from charge injection of the excited surface modifiers could be quenched by switching the poling bias from +8 V to −8 V.
Super‐Resolution Imaging of Plasma Membrane Glycans
Authors: Letschert Sebastian , Göhler Antonia , Franke Christian , Bertleff‐Zieschang Nadja , Memmel Elisabeth , Doose Sören , Seibel Jürgen , Sauer Markus
Published: August 2014

Much of the physiology of cells is controlled by the spatial organization of the plasma membrane and the glycosylation patterns of its components, however, studying the distribution, size, and composition of these components remains challenging. A bioorthogonal chemical reporter strategy was used for the efficient and specific labeling of membrane‐associated glycoconjugates with modified monosaccharide precursors and organic fluorophores. Super‐resolution fluorescence imaging was used to visualize plasma membrane glycans with single‐molecule sensitivity. Our results demonstrate a homogeneous distribution of N‐acetylmannosamine (ManNAc)‐, N‐acetylgalactosamine (GalNAc)‐, and O‐linked N‐acetylglucosamine (O‐GlcNAc)‐modified plasma membrane proteins in different cell lines with densities of several million glycans on each cell surface.
Dialdehydes Lead to Exceptionally Fast Bioconjugations at Neutral pH by Virtue of a Cyclic Intermediate
Authors: Schmidt Pascal , Zhou Linna , Tishinov Kiril , Zimmermann Kaspar , Gillingham Dennis
Published: August 2014

One of the open challenges in chemical biology is to identify reactions that proceed with large rate constants at neutral pH values. As shown here, dialdehydes react with O‐alkylhydroxylamines at rates of 500 M−1 s−1 at neutral pH values in the absence of catalysts. The key to these conjugations is an unusually stable cyclic intermediate, which ultimately undergoes dehydration to yield an oxime. The scope and limitations of the method are outlined, as well as its application in bioconjugation and a mechanistic interpretation that will facilitate further developments of reactions with alkylhydroxylamines at low substrate concentrations.
Wood‐derived phenol novolaks and their wood/epoxy biocomposites
Authors: Enjoji Motohiro , Yamamoto Asami , Shibata Mitsuhiro
Published: August 2014

Guaiacol novolak (GCN) and wood‐tar creosote novolak (WCN) were synthesized by the reactions of wood‐derived guaiacol and creosote with formalin, respectively, and used as hardeners of sorbitol polyglycidyl ether (SPE). Thermal and mechanical properties of the cured resins (SPE‐GCN and SPE‐WCN) and their biocomposites with wood flour (WF) were compared with those of the materials prepared by using a petroleum‐based phenol novolak (PN). Although tan δ peak temperatures of SPE‐GCN and SPE‐WCN were lower than that of SPE‐PN, that (58.5–70.8°C) of SPE‐GCN/WF(40–50 wt %) was higher than that (56.6–57.0°C) of SPE‐PN/WF(40–50 wt %). Tensile moduli of all the biocomposites increased by the addition of WF, while tensile strengths were rather reduced. When the biocomposites with the same WF content were compared, tensile modulus of SPE‐GCN/WF was higher than that of SPE‐PN/WF. The 5% weight loss temperatures (346–291°C) of SPE‐GCN and SPE‐GCN/WF were comparable to those (338–284°C) of SPE‐PN and SPE‐PN/WF. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41347.
Effects of melt structure on crystallization behavior of isotactic polypropylene nucleated with α/β compounded nucleating agents
Authors: Zhang Qiyan , Chen Zhengfang , Wang Bing , Chen Jinyao , Yang Feng , Kang Jian , Cao Ya , Xiang Ming , Li Huilin
Published: August 2014

In this study, the melt structure of isotactic polypropylene (iPP) nucleated with α/β compounded nucleating agents (α/β‐CNA, composed of the α‐NA of 0.15 wt % Millad 3988 and the β‐NA of 0.05 wt % WBG‐II) was tuned by changing the fusion temperature Tf. In this way, the role of melt structure on the crystallization behavior and polymorphic composition of iPP were investigated by differential scanning calorimetry (DSC), wide‐angle X‐ray scattering (WAXD) and scanning electron microscopy (SEM). The results showed that when Tf = 200°C (iPP was fully molten), the α/β‐CNA cannot encourage β‐phase crystallization since the nucleation efficiency (NE) of the α‐NA 3988 was obviously higher than that of the β‐NA WBG‐II. Surprisingly, when Tf was in 179–167°C, an amount of ordered structures survived in the melt, resulting in significant increase of the proportion of β‐phase (achieving 74.9% at maximum), indicating that the ordered structures of iPP played determining role in β‐phase crystallization of iPP nucleated with the α/β‐CNA. Further investigation on iPP respectively nucleated with individual 3988 and WBG‐II showed that as Tf decreased from 200°C to 167°C, the crystallization peak temperature Tc of iPP/3988 stayed almost constant, while Tc of iPP/WBG‐II increased gradually when Tf < 189°C and became higher than that of iPP/3988 when Tf decreased to 179°C and lower, which can be used to explain the influence of ordered structure and α/β‐CNA on iPP crystallization. Using this method, the selection of α‐NA for α/β‐CNA can be greatly expanded even if the inherent NE of β‐NA is lower than that of the α‐NA. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41355.
The role of the interphase on the shear induced failure of multiwall carbon nanotubes reinforced epoxy nanocomposites
Authors: Chiacchiarelli Leonel Matías , Escobar Mariano Martín , Kenny José María , Torre Luigi , Vazquez Analía
Published: August 2014

Multiwall Carbon Nanotubes (MWCNT) with an elevated aspect ratio were chemically functionalized with amines and two types of epoxide groups. Thermogravimetric analysis and Fourier Transform‐Infrared Spectroscopy (FTIR) analysis corroborated that the functionalization degree was substantial (up to 30 wt %) and the presence of a covalent bond with the MWCNT. The functionalized MWCNT (f‐CNT) were incorporated into an epoxy matrix after its dispersion in the diglycidyl ether of bisphenol A (DGEBA) precursor. To induce a shear failure mode, a short‐beam (SB) experimental setup was implemented. The SB shear strength (SBSS) proved that the functionalization had a strong influence on its value. For the case of pristine CNT, a neutral effect was obtained. A strong detrimental effect (−17.2% ± 9.5) was measured for the amine type f‐CNT and a positive effect (up to 10.9% ± 8.9) was measured of the epoxide type f‐CNT. Fractographic analysis of each formulation was correlated with SBSS performance, proving that the surface texture of the fractured samples was strongly correlated to its value. Furthermore, dynamic mechanical analysis proved that the damping factor and the crosslink molecular weight were correlated with the SBSS performance. A lower full width at half maximum of the damping factor was associated to an improvement of SBSS. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41364.
Random and aligned PLLA : PRGF electrospun scaffolds for regenerative medicine
Authors: Díaz‐Gómez Luis , Ballarin Florencia Montini , Abraham Gustavo A. , Concheiro Angel , Alvarez‐Lorenzo Carmen
Published: August 2014

Random and aligned electrospun scaffolds were prepared combining poly(l‐lactic acid) (PLLA) and activated platelet‐rich plasma (PRGF) at various proportions, with the aim of elucidating the role of nanofibers orientation and growth factors on cell attachment and proliferation. PRGF is released from scaffolds in a sustained way for at least 3 weeks, without an initial burst effect. Mesenchymal stem cells (MSCs) seeded on the random scaffolds present a polygonal and random orientation in any direction of the scaffold. On the other hand, aligned scaffolds are able to promote cell attachment and proliferation in the direction of the nanofibers. The incorporation of PRGF in the scaffolds enhances cell proliferation for at least 2 weeks. Overall, aligned electrospun PLLA : PRGF scaffolds can encapsulate growth factors at relatively large proportions and sustain their release to enhance cell attachment and proliferation as well as eliciting cell alignment. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2015,132, 41372.
Design, Synthesis, and Local Anti‐Inflammatory Activity of 17β‐Carboxamide Derivatives of Glucocorticoids
Authors: Dobričić Vladimir , Marković Bojan , Milenković Nikola , Savić Vladimir , Jaćević Vesna , Rančić Nemanja , Vladimirov Sote , Čudina Olivera
Published: August 2014

Molecular docking studies were performed on 18 17β‐carboxamide steroids in order to select compounds with potential local anti‐inflammatory activity. These derivatives are amides of cortienic acids (obtained from hydrocortisone, prednisolone, and methylprednisolone) with methyl or ethyl esters of six amino acids. Interactions with the glucocorticoid receptor (GR), binding energies and ligand efficiency values of these compounds were compared with dexamethasone and cortienic acid obtained from prednisolone (inactive metabolite). On the basis of molecular docking studies, seven compounds were selected and their binding affinities for the GR were predicted by use of the exponential model created in this study. Subsequently, selected compounds were synthesized in good yields by use of modified N,N′‐dicyclohexylcarbodiimide (DCC)/1‐hydroxybenzotriazole (HOBt) coupling procedure. Finally, the local anti‐inflammatory activity of the synthesized compounds was examined by use of the croton oil‐induced ear edema test. In vivo evaluation of systemic side effects as well as in silico prediction of metabolism were performed on the derivative with the best local anti‐inflammatory activity. The combination of molecular docking studies and the exponential model for the GR binding affinity prediction could be used as an in silico tool for the rational design of novel 17β‐carboxamide steroids with potentially better biological profile than dexamethasone.
Rationally Designed Less Toxic SPD‐304 Analogs and Preliminary Evaluation of Their TNF Inhibitory Effects
Authors: Alexiou Polyxeni , Papakyriakou Athanasios , Ntougkos Evangelos , Papaneophytou Christos P. , Liepouri Fotini , Mettou Anthi , Katsoulis Ioannis , Maranti Anna , Tsiliouka Katerina , Strongilos Alexandros , Chaitidou Sotiria , Douni Eleni , Kontopidis George , Kollias George , Couladouros Elias , Eliopoulos Elias
Published: August 2014

SPD‐304 was discovered as a promising tumor necrosis factor alpha (TNF) antagonist that promotes dissociation of TNF trimers and therefore blocks the interaction of TNF and its receptor. However, SPD‐304 contains a potentially toxic 3‐alkylindole moiety, which can be bioactivated to a reactive electrophilic intermediate. A series of SPD‐304 analogs was synthesized with the aim to diminish its toxicophore groups while maintaining the binding affinity for TNF. Incorporation of electron‐withdrawing substituents at the indole moiety, in conjunction with elimination of the 6′‐methyl group of the 4‐chromone moiety, led to a significantly less toxic and equally potent TNF inhibitor.
The use of gait parameters to evaluate pedestrian behavior at scramble phase signalized intersections
Authors: Hediyeh Houman , Sayed Tarek , Zaki Mohamed H.
Published: August 2014

Pedestrian scramble phasing is usually implemented to reduce pedestrian‐vehicle conflicts and therefore increase the safety of the intersection. However, to adequately determine the benefits of scramble phasing, it is necessary to understand how pedestrians react to such an unconventional design. This study investigates changes in pedestrian crossing behavior following the implementation of a scramble phase by examining the spatiotemporal gait parameters (step length and step frequency). This detailed microscopic‐level analysis provides insight into changes in pedestrian walking mechanisms as well as the effect of various pedestrian and intersection characteristics. The study uses video data collected at a scramble phase signalized intersection in Oakland, California. Gait parameters were found to be influenced by pedestrian gender, age, group size, crosswalk length, and pedestrian signal indications. Both average step length and walking speed were significantly higher for diagonally crossing pedestrians compared with pedestrians crossing on the conventional crosswalks. Pedestrians were found to have the tendency to increase their step length more than their step frequency to increase walking speed. It was also found that, compared with men, women generally increase their walking speed by increasing their step frequency more than step length. However, when in non‐compliance with signal indications, women increase their walking speed by increasing their step length more than step frequency. It was also found that older pedestrians do not significantly change their walking behavior when in non‐compliance with signal indications. Copyright © 2014 John Wiley & Sons, Ltd.
Formation of fluorescent carbon nanodots from kitchen wastes and their application for detection of Fe3+
Authors: Xu Jinjin , Lai Tiantian , Feng Zhiling , Weng Xuexiang , Huang Chaobiao
Published: August 2014

This work reports a scalable synthesis of water‐dispersible fluorescent carbon nanodots based on the simple hydrothermal method (180 °C for 6 h) of kitchen wastes (grape peel for example). We discuss the feasibility of synthesis from kitchen wastes both experimentally and theoretically, and the as‐prepared nanodots have high selectivity for Fe3+ ions based on fluorescence quenching which is due to the complexes between nanodots and metal ions. Copyright © 2014 John Wiley & Sons, Ltd.
The Role of Neglect in Child Fatality and Serious Injury
Authors: Brandon Marian , Bailey Sue , Belderson Pippa , Larsson Birgit
Published: August 2014

Although there is improved recognition of the pernicious long‐term harm that stems from living with neglect during childhood, neglect is rarely associated with child fatality. This article offers a re‐analysis of neglect in serious case reviews (cases of child death or serious injury related to maltreatment) in England (2003–11) from four consecutive government‐commissioned national two‐yearly studies. It draws on anonymised research information from 46 cases out of a total of over 800 cases. Each case was examined in depth using an ecological transactional approach, grounded in the child's experience, which promotes a dynamic understanding and assessment of the interactions between children and their families and the helping practitioners. The qualitative findings reported explore how circumstances came together when neglect had a catastrophic impact on the child and family presenting in six different ways (deprivational neglect, medical neglect, accidents with elements of forewarning, sudden unexpected deaths in infancy, physical abuse combined with neglect and young suicide). Each of the six categories raised particular issues over and above a common core of concerns around the relationship between the child and his or her parent or carer, and between parents/carers and professionals. © 2014 The Authors. Child Abuse Review published by John Wiley & Sons Ltd.

‘neglect is rarely associated with child fatality’

‘Each of the six categories raised particular issues’

Key Practitioner Messages:

There are no easy answers to curbing potentially fatal neglect – practitioners should be supported to make careful well‐reasoned judgements.

That neglect is not only harmful but can also be fatal should be part of any practitioner's mindset, as with other maltreatment.

To guard against catastrophic neglect, children need to be physically and emotionally healthy and have a safe, healthy living environment.

Practitioners need to be compassionate and sensitively attuned to the relationship between parents and children.

‘practitioners need to be compassionate and sensitively attuned to the relationship between parents and children.’
Working Effectively with Neglected Children and Their Families – What Needs To Change?
Authors: Farmer Elaine , Lutman Eleanor
Published: August 2014

Since practitioners have little research to inform them about how to keep neglected children safe and improve their outcomes, we conducted a study about how risks are managed over time. The research in seven local authorities involved 138 neglected children who were returned from care to their parents and followed up for another five years through reviews of case files and interviews with social workers.

‘We conducted a study about how risks are managed over time’

Work with neglected children and their families was dogged by ‘inescapable errors’, which we argue will always occur in work over time and need to be deliberately interrupted. Parents were difficult to engage, and over time abuse and neglect were often minimised so that referrals about harm to children did not lead to sufficient protective action. Parents were given too many chances to change, and files lacked information on the development of children on which decisions about intervention could be based. Using written contracts with parents would assist practitioners to assess parental capacity to make the changes required. A new approach to working with neglected children is required which will allow patterns of children's developmental and other progress to be recognised over time, rooted in collecting evidence which could be used in care proceedings if required. Copyright © 2014 John Wiley & Sons, Ltd.

‘A new approach is required which will allow patterns of children's developmental and other progress to be recognised over time’

Key Practitioner Messages

A new approach to working with neglected children is required which will chart patterns of children's developmental and other progress so that they can be recognised over time – rooted in collecting evidence which could be used in care proceedings if required.

Using written contracts with parents would assist practitioners to assess parental capacity to make the changes required to keep children safe and allow them to develop normally.

‘Using written contracts with parents would assist practitioners to assess parental capacity to make the changes required’
Transforming a Wild World: Helping Children and Families to Address Neglect in the Province of Quebec, Canada
Authors: Lacharité Carl
Published: August 2014

Neglect is a complex social problem with serious consequences for the fulfilment of the needs of a child by adults in the child's immediate family and social network – not only parents, but other adults who come into contact with the child (including professionals). However, child protection systems have difficulty taking into account the social nature and the relational complexity of this issue. In fact, they have, consequently, a tendency to concentrate on the parents' deficiencies with regard to their responsibility to their children. This article describes the theoretical foundation of an ecosystemic and developmental model that forms the basis for the development of integrated child neglect services in Quebec, Canada. It also describes the components and activities that aim to operationalise this ecosystemic and developmental model of child neglect. Copyright © 2014 John Wiley & Sons, Ltd.

‘This article describes the theoretical foundation of an ecosystemic and developmental model’

Key Practitioner Messages:

Child neglect is characterised by the collapse of the social organisation surrounding children and their parents.

Social action targeting neglect must be based on:

an ecosystemic and developmental understanding of the child's needs and the parents' responsibilities;

a participatory approach involving parents and children;

allowance for the parents' experience of their role in the development of their children;

the creation of normative developmental experiences for the children.

‘Child negelct is characterised by the collapse of the social organisation surrounding children and their parents’
Organotin–Oxido Cluster‐Based Multiferrocenyl Complexes Obtained by Hydrolysis of Ferrocenyl‐Functionalized Organotin Chlorides
Authors: You Zhiliang , Möckel Robert , Bergunde Jakob , Dehnen Stefanie
Published: August 2014

Three organotin–oxido clusters were formed by hydrolysis of ferrocenyl‐functionalized organotin chloride precursors in the presence of NaEPh (E=S, Se). [RFcSnCl3⋅HCl] (C; RFc = CMe2CH2C(Me)NNC(Me)Fc) and [SnCl6]2− formed {(RFcSnCl2)3[Sn(OH)6]}[SnCl3] (3 a) and {(RFcSnCl2)3[Sn(OH)6]}[PhSeO3] (3 b), bearing an unprecedented [Sn4O6] unit, in a one‐pot synthesis or stepwise through [(RFcSnCl2)2Se] (1) plus [(RFcSnCl2)SePh] (2). A one‐pot reaction starting out from FcSnCl3 gave [(FcSn)9(OH)6O8Cl5] (4), which represents the largest Fc‐decorated Sn/O cluster reported to date.
Mechanical effects of EB1 on microtubules depend on GTP hydrolysis state and presence of paclitaxel
Authors: Lopez Benjamin J. , Valentine Megan T.
Published: August 2014

Using the nonhydrolyzable GTP analog GMPCPP and the slowly hydrolyzable GTPγS, we polymerize microtubules that recapitulate the end binding behavior of the plus end interacting protein (+TIP) EB1 along their entire length, and use these to investigate the impact of EB1 binding on microtubule mechanics. To measure the stiffness of single filaments, we use a spectral analysis method to determine the ensemble of shapes adopted by a freely diffusing, fluorescently labeled microtubule. We find that the presence of EB1 can stiffen microtubules in a manner that depends on the hydrolysis state of the tubulin‐bound nucleotide, as well as the presence of the small‐molecule stabilizer paclitaxel. We find that the magnitude of the EB1‐induced stiffening is not proportional to the EB1‐microtubule binding affinity, suggesting that the stiffening effect does not arise purely from an increase in the total amount of bound EB1. Additionally, we find that EB1 binds cooperatively to microtubules in manner that depends on tubulin‐bound nucleotide state. © 2014 Wiley Periodicals, Inc.
The Importance of Hydration Thermodynamics in Fragment‐to‐Lead Optimization
Authors: Ichihara Osamu , Shimada Yuzo , Yoshidome Daisuke
Published: August 2014

Using a computational approach to assess changes in solvation thermodynamics upon ligand binding, we investigated the effects of water molecules on the binding energetics of over 20 fragment hits and their corresponding optimized lead compounds. Binding activity and X‐ray crystallographic data of published fragment‐to‐lead optimization studies from various therapeutically relevant targets were studied. The analysis reveals a distinct difference between the thermodynamic profile of water molecules displaced by fragment hits and those displaced by the corresponding optimized lead compounds. Specifically, fragment hits tend to displace water molecules with notably unfavorable excess entropies—configurationally constrained water molecules—relative to those displaced by the newly added moieties of the lead compound during the course of fragment‐to‐lead optimization. Herein we describe the details of this analysis with the goal of providing practical guidelines for exploiting thermodynamic signatures of binding site water molecules in the context of fragment‐to‐lead optimization.
On the Origin of Damped Electrochemical Oscillations at Silicon Anodes (Revisited)
Authors: Proost Joris , Blaffart Frédéric , Turner Stuart , Idrissi Hosni
Published: August 2014

Electrochemical oscillations accompanying the formation of anodic silica have been shown in the past to be correlated with rather abrupt changes in the mechanical stress state of the silica film, commonly associated with some kind of fracture or porosification of the oxide. To advance the understanding on the origin of such oscillations in fluoride‐free electrolytes, we have revisited a seminal experiment reported by Lehmann almost two decades ago. We thereby demonstrate that the oscillations are not stress‐induced, and do not originate from a morphological transformation of the oxide in the course of anodisation. Alternatively, the mechanical features accompanying the oscillations can be explained by a partial relaxation of the field‐induced electrostrictive stress. Furthermore, our observations suggest that the oscillation mechanism more likely results from a periodic depolarisation of the anodic silica.
A Computational Study on 3‐Azonia‐, 3‐Phosphonia‐, and 3‐Arsoniaspiro[2.2]pentanes and Related Three‐Membered Heterocycles
Authors: Trujillo Cristina , Sánchez‐Sanz Goar , Alkorta Ibon , Elguero José
Published: August 2014

A theoretical study at the ab initio MP2/6‐311++G(d,p) level of theory is carried out to characterize several heterocyclic spiro[2.2]pentane cations with N, P, and As as spiro atoms. The strain and relative stability of the spiropentanes are obtained through isodesmic reactions. Nucleus‐independent chemical shifts (NICS) and 3D NICS isosurfaces show σ‐aromatic characteristics, similar to those found in cyclopropane. The interaction with the Cl−anion, which results in four different stationary structures, is studied and characterized by means of the atoms in molecules methodology, and Cl⋅⋅⋅pnicogen, Cl⋅⋅⋅H, and Cl⋅⋅⋅C interactions are found. The most stable structure in all cases corresponds to opening of one of the three‐membered rings, due to the attack of the Cl atom, and CCl bond formation. Furthermore, the reaction with the 3‐boranuidaspiro[2.2]pentane anion results in the formation of a new compound through cleavage of one ring of both reactants.
Palladium Nanoparticles Supported on Vertically Oriented Reduced Graphene Oxide for Methanol Electro‐Oxidation
Authors: Yang Liming , Tang Yanhong , Luo Shenglian , Liu Chengbin , Song Hejie , Yan Dafeng
Published: August 2014

Reduced graphene oxide (rGO) is a promising support material for nanosized electrocatalysts. However, the conventional stacking arrangement of rGO sheets confines the electrocatalysts between rGO layers, which decreases the number of catalytic sites substantially. We report here a facile synthesis of vertically oriented reduced graphene oxide (VrGO) through cyclic voltammetric electrolysis of graphene oxide (GO) in the presence of Na2PdCl4. Experiments without Pd nanoparticles or with a low loading amount of Pd nanoparticles results in the deposition of rGO parallel to the electrodes. The vertical orientation of Pd/rGO nanoflakes causes a remarkable enhancement of the catalytic activity toward methanol electro‐oxidation. The mass activity (620.1 A gPd−1) of Pd/VrGO is 1.9 and 6.2 times that of Pd/flat‐lying rGO (331.8 A gPd−1) and commercial Pd/C (100.5 A gPd−1), respectively. Furthermore, the Pd/VrGO catalyst shows excellent resistance to CO poisoning. This work provides a simple wet‐chemical method for VrGO preparation.
A Facile and Green Method to Hydrophobize Films of Cellulose Nanofibrils and Silica by Laccase‐Mediated Coupling of Nonpolar Colloidal Particles
Authors: Cusola Oriol , Roncero M. Blanca , Vidal Teresa , Rojas Orlando J.
Published: August 2014

Hydrophobic particles based on dodecyl 3,4,5‐trihydroxybenzoate (LG) were coupled onto the surface of cellulose nanofibrils (CNFs) and silica by treatment with a multicomponent colloidal system (MCS) derived from the laccase‐mediated reaction of LG in the presence of a sulfonated lignin (SL). Surface modification upon treatment with MCS was monitored in situ and in real time by quartz crystal microgravimetry. The colloidal stability of MCS and its components in water was followed by measuring space‐ and time‐resolved light transmission and back scattering. The sulfonated lignin increased dispersion stability and reduced the characteristic MCS particle size [from ≈4 to ≈80 nm, according to AFM and dynamic light scattering (DLS)]. It also facilitated the surface enzymatic reaction that led to adsorption and coupling of MCS onto CNFs and silica surfaces. The combined effect of reduced surface energy and surface roughness by MCS treatment produced an increase in water contact angle on CNFs and silica of about 90 and 80°, respectively. Surface pretreatment with chitosan further increased the extent of MCS adsorption on the surfaces. This method represents a sustainable alternative to traditional approaches for cellulose hydrophobization and a step forward in implementing green routes for surface modification.