bluuebunny/crossref_metadata_2025 huggingface dataset:
L’AGRESSIVITÉ EXCESSIVE CHEZ LE JEUNE ENFANT : ÉTUDE DES TROUBLES CLINIQUES ET DES ATTITUDES PARENTALES
Authors: Urbain-Gauthier Nadine , Wendland Jaqueline
Published: August 2017

L’agressivité physique excessive chez les jeunes enfants est un problème important en santé mentale, entraînant des dysfonctionnements en famille et en collectivité, voire l’exclusion sociale précoce. Les objectifs de cette étude sont de : a) spécifier les troubles cliniques chez 60 jeunes enfants, âgés de moins de 5 ans, orientés pour de l’agressivité excessive ainsi que leur profil développemental; b) cerner les caractéristiques des attitudes parentales et les articuler avec les profils développementaux des enfants. Les résultats sont discutés en termes des stratégies thérapeutiques adaptées qui peuvent être proposées pour aider ces enfants et leurs parents.
Circular oligomerization is an intrinsic property of synaptotagmin
Authors: Wang Jing , Li Feng , Bello Oscar D , Sindelar Charles Vaughn , Pincet Frédéric , Krishnakumar Shyam S , Rothman James E
Published: August 2017

Previously, we showed that synaptotagmin1 (Syt1) forms Ca2+-sensitive ring-like oligomers on membranes containing acidic lipids and proposed a potential role in regulating neurotransmitter release (Zanetti et al., 2016). Here, we report that Syt1 assembles into similar ring-like oligomers in solution when triggered by naturally occurring polyphosphates (PIP2 and ATP) and magnesium ions (Mg2+). These soluble Syt1 rings were observed by electron microscopy and independently demonstrated and quantified using fluorescence correlation spectroscopy. Oligomerization is triggered when polyphosphates bind to the polylysine patch in C2B domain and is stabilized by Mg2+, which neutralizes the Ca2+-binding aspartic acids that likely contribute to the C2B interface in the oligomer. Overall, our data show that ring-like polymerization is an intrinsic property of Syt1 with reasonable affinity that can be triggered by the vesicle docking C2B-PIP2 interaction and raise the possibility that Syt1 rings could pre-form on the synaptic vesicle to facilitate docking.
Validation and description of two new north-western Australian Rainbow skinks with multispecies coalescent methods and morphology
Authors: Afonso Silva Ana C. , Santos Natali , Ogilvie Huw A. , Moritz Craig
Published: August 2017

While methods for genetic species delimitation have noticeably improved in the last decade, this remains a work in progress. Ideally, model based approaches should be applied and considered jointly with other lines of evidence, primarily morphology and geography, in an integrative taxonomy framework. Deep phylogeographic divergences have been reported for several species ofCarliaskinks, but only for some eastern taxa have species boundaries been formally tested. The present study does this and revises the taxonomy for two species from northern Australia,Carlia johnstoneiandC. triacantha. We introduce an approach that is based on the recently published method StarBEAST2, which uses multilocus data to explore the support for alternative species delimitation hypotheses using Bayes Factors (BFD). We apply this method, jointly with two other multispecies coalescent methods, using an extensive (from 2,163 exons) data set along with measures of 11 morphological characters. We use this integrated approach to evaluate two new candidate species previously revealed in phylogeographic analyses of rainbow skinks (genusCarlia) in Western Australia. The results based on BFD StarBEAST2, BFD* SNAPP and BPP genetic delimitation, together with morphology, support each of the four recently identifiedCarlialineages as separate species. The BFD StarBEAST2 approach yielded results highly congruent with those from BFD* SNAPP and BPP. This supports use of the robust multilocus multispecies coalescent StarBEAST2 method for species delimitation, which does not requirea prioriresolved species or gene trees. Compared to the situation inC. triacantha, morphological divergence was greater between the two lineages within Kimberley endemicC. johnstonei, which also had deeper divergent histories. This congruence supports recognition of two species withinC. johnstonei. Nevertheless, the combined evidence also supports recognition of two taxa within the more widespreadC. triacantha. With this work, we describe two new species,Carlia insularissp. nov andCarlia isostriacanthasp. nov. in the northwest of Australia. This contributes to increasing recognition that this region of tropical Australia has a rich and unique fauna.
Do Autoemprego ao Microempreendedorismo Individual: Desafios Conceituais e Empíricos
Authors: Colbari Antonia De Lourdes
Published: August 2017

Trata-se de um estudo exploratório sobre aspectos do processo de institucionalização da categoria trabalhador por conta própria ou trabalhador autônomo (expressões utilizadas para designar o autoemprego), juridicamente incorporado como microempreendedor individual (MEI). Apesar das lacunas do suporte empírico, o tratamento descritivo dos dados à luz de um recorte no corpus do debate sobre informalidade e empreendedorismo aflorou algumas reflexões: a conjunção preferência e/ou constrangimento na inserção produtiva fora do regime salarial; a complexidade de motivações manifestas e latentes embutidas na iniciativa de formalizar uma parcela de trabalhadores historicamente associada à informalidade; o delineamento do perfil do MEI; e as problematizações sobre o significado desse fenômeno em que o autoemprego se institucionaliza pela via da “empresarialidade”, na categoria de empreendedor individual (o autoempresariamento).
Racionalidades na Dinâmica da Produção Pesqueira: A Percepção dos Pescadores Artesanais da Grande Florianópolis diante do Quadro de Degradação Socioambiental do Litoral Catarinense
Authors: De Oliveira Menezes Elaine Cristina , Ronconi Luciana
Published: August 2017

O processo de urbanização desordenado do litoral catarinense e a degradação ambiental vêm trazendo inúmeros malefícios à vida sustentável dos pescadores e da própria pesca artesanal, principalmente na região da Grande Florianópolis. O presente artigo pretendeu avaliar o tipo de racionalidades presentes na dinâmica da produção pesqueira e a percepção dos pescadores artesanais quanto à sustentabilidade da sua atividade na região. A pesquisa valeu-se de uma abordagem qualitativa, por meio de entrevistas semiestruturadas com 25 atores-chave. Concluiu-se que a racionalidade predominante é a do cálculo utilitário, cujas consequências são a exploração abusiva dos recursos pesqueiros e a ausência de mecanismos de gestão compartilhada e negociada desses recursos. A racionalidade substantiva, embora presente nas dinâmicas produtivas da pesca artesanal, não tem tido impacto significativo sobre a gestão dos recursos pesqueiros locais. 
Prefrontal bore mixing
Authors: van Haren Hans , Duineveld Gerard , de Stigter Henko
Published: August 2017

Rainbow Ridge, a 1950 m deep upthrusted ultramafic block along the axis of the Mid‐Atlantic Ridge, has an active hydrothermal vent system at 2400 m on its western slope. However, within 1 km from the vent excessive temperatures are barely measurable, probably due to strong turbulent mixing. This mixing is studied here using a 400 m long high‐resolution temperature sensor array moored with a 600 m ranging 75 kHz acoustic Doppler current profiler. Rich internal wave turbulence was recorded, characterized by 100–200 m upshoots and >200 m large overturning in particular near the end of the warming phase of the up and down moving tide. These highly nonlinear internal waves of tides interacting with buoyancy frequency waves extend up to 400 m above the sloping bottom of the ridge. While a turbulent “bottom boundary layer” could barely be defined, the more intense turbulence higher up in the water column is suggested to lead to the strong dispersion of the hydrothermal plume.
Aeromagnetic, gravity, and Differential Interferometric Synthetic Aperture Radar analyses reveal the causative fault of the 3 April 2017 Mw 6.5 Moiyabana, Botswana, earthquake
Authors: Kolawole F. , Atekwana E. A. , Malloy S. , Stamps D. S. , Grandin R. , Abdelsalam M. G. , Leseane K. , Shemang E. M.
Published: August 2017

On 3 April 2017, a Mw 6.5 earthquake struck Moiyabana, Botswana, nucleating at >20 km focal depth within the Paleoproterozoic Limpopo‐Shashe orogenic belt separating the Archean Zimbabwe and Kaapvaal Cratons. We investigate the lithospheric structures associated with this earthquake using high‐resolution aeromagnetic and gravity data integrated with Differential Interferometric Synthetic Aperture Radar (DInSAR) analysis. Here we present the first results that provide insights into the tectonic framework of the earthquake. The ruptured fault trace delineated by DInSAR aligns with a distinct NW striking and NE dipping magnetic lineament within the Precambrian basement. The fault plane solution and numerical modeling indicate that the cause of the earthquake was 1.8 m displacement along a NW striking and NE dipping normal fault, rupturing at 21–24 km depth. We suggest that this seismic event was due to extensional reactivation of a crustal‐scale Precambrian thrust splay within the Limpopo‐Shashe orogenic belt.
Aspect dependence of Langmuir parametric instability excitation observed by EISCAT
Authors: Wang Xiang , Zhou Chen
Published: August 2017

Recent studies of X‐mode wave heating experiments observed by EISCAT (European Incoherent Scatter Scientific Association UHF radar indicate that parametric instability (PI) can be excited unexpectedly. In this paper, we reinvestigate the ionospheric heating experiment on 21 and 22 October 2012 in details. The observed HF‐enhanced ion lines (HFILs) and HF‐enhanced plasma lines (HFPLs) observed during the experiments present dependence on the heating incidence angles. The observational evidence and numerical calculation that the parallel electric field of X‐mode heating wave can exceed the PI excitation threshold at certain angles indicate the decisive role of parallel electric field for the PI excitation. The excited HFPLs and HFILs during X‐mode heating cycles also present the evidence for the non‐Maxwellian distribution of the electrons in the heated region.
2017 Valparaíso earthquake sequence and the megathrust patchwork of central Chile
Authors: Nealy Jennifer L. , Herman Matthew W. , Moore Ginevra L. , Hayes Gavin P. , Benz Harley M. , Bergman Eric A. , Barrientos Sergio E.
Published: August 2017

In April 2017, a sequence of earthquakes offshore Valparaíso, Chile, raised concerns of a potential megathrust earthquake in the near future. The largest event in the 2017 sequence was a M6.9 on 24 April, seemingly colocated with the last great‐sized earthquake in the region—a M8.0 in March 1985. The history of large earthquakes in this region shows significant variation in rupture size and extent, typically highlighted by a juxtaposition of large ruptures interspersed with smaller magnitude sequences. We show that the 2017 sequence ruptured an area between the two main slip patches during the 1985 earthquake, rerupturing a patch that had previously slipped during the October 1973 M6.5 earthquake sequence. A significant gap in historic ruptures exists directly to the south of the 2017 sequence, with large enough moment deficit to host a great‐sized earthquake in the near future, if it is locked.
Dynamic response of the Martian ionosphere to an interplanetary shock: Mars Express and MAVEN observations
Authors: Harada Y. , Gurnett D. A. , Kopf A. J. , Halekas J. S. , Ruhunusiri S. , Lee C. O. , Hara T. , Espley J. , DiBraccio G. A. , Mitchell D. L. , Mazelle C. , Larson D. E. , Jakosky B. M.
Published: August 2017

Multipoint observations from the Mars Advanced Radar for Subsurface and Ionosphere Sounding (MARSIS) instrument on board Mars Express and the Mars Atmosphere and Volatile EvolutioN (MAVEN) mission reveal a dynamic response of the Martian ionosphere to abrupt variations in the upstream solar wind plasma. On 2 February 2017, MAVEN, located upstream from the Martian bow shock, encountered a corotating interaction region‐related interplanetary shock with a sudden enhancement in the dynamic pressure. MARSIS, operating in the upper ionosphere at ∼478 km altitudes and ∼78° solar zenith angles, observed a sharp increase in the local magnetic field magnitude ∼1 min after the shock passage at MAVEN. The time lag is roughly consistent with the expected propagation time of a pressure pulse from the bow shock to the upper ionosphere at the fast magnetosonic speed. Subsequently, remote soundings recorded disturbed signatures of the topside ionosphere below Mars Express.
The relationship between contrasting ages of groundwater and streamflow
Authors: Berghuijs Wouter R. , Kirchner James W.
Published: August 2017

Tracer data demonstrate that waters in aquifers are often much older than the stream waters that drain them. This contrast in water ages has lacked a general quantitative explanation. Here we show that under stationary conditions, the age distribution of water stored in a catchment can be directly estimated from the age distribution of its outflows, and vice versa. This in turn implies that the storage selection function, expressing the catchment's preference for the release or retention of waters of different ages, can be estimated directly from the age distribution of outflow under stationary conditions. Using gamma distributions of streamflow ages, we show that the mean age of stored water can range from half as old as the mean age of streamflow (for plug flow conditions) to almost infinitely older (for strongly preferential flow). Many streamflow age distributions have long upper tails, consistent with preferential flow and implying that storage ages are substantially older than streamflow ages. Mean streamflow ages reported in the literature imply that most streamflow originates from a thin veneer of total groundwater storage. This preferential release of young streamflow implies that most groundwater is exchanged only slowly with the surface and consequently is relatively old.
Tuning Thermal Transport in Chain‐Oriented Conducting Polymers for Enhanced Thermoelectric Efficiency: A Computational Study
Authors: Shi Wen , Shuai Zhigang , Wang Dong
Published: August 2017

Thermoelectric polymers should be electron‐crystal and phonon‐glass to efficiently interconvert heat and electricity. Herein, by using molecular dynamics simulations, it is demonstrated that engineering phonon transport in conducting polymers by tailoring its degree of polymerization can effectively improve the energy conversion efficiency. This is based on the separated length scales that charge carriers and phonons travel along the polymer backbone. By tuning the chain length and the crystallinity of chain‐oriented poly(3,4‐ethylenedioxythiophene) fibers, a dramatic decrease of the axial thermal conductivity to 0.97 W m−1 K−1 has been observed in rationally designed polymer fibers with the crystallinity of 0.49 and the relative molecular weight of 5600. The dimensionless thermoelectric figure of merit at 298 K has been enhanced to 0.48, which is approximately one order of magnitude higher than that in crystalline polymers.
Giant Incident Photon‐to‐Current Conversion with Photoconductivity Gain on Nanostructured Bismuth Oxysulfide Photoelectrodes under Visible‐Light Illumination
Authors: Bondarenko Evgeny A. , Streltsov Eugene A. , Malashchonak Mikalai V. , Mazanik Alexander V. , Kulak Anatoly I. , Skorb Ekaterina V.
Published: August 2017

Nanostructured layered bismuth oxysulfide films synthesized by chemical bath deposition reveal a giant incident photon‐to‐current conversion efficiency (IPCE). This study shows that surprisingly for the cathodic photocurrent in the photoreduction process, the IPCE reaches ≈2500% in aqueous solutions containing [Fe(CN)6]3−. The giant IPCE is observed starting from a certain minimal oxidizer concentration (c > 10−3m for [Fe(CN)6]3−) and decreases nonlinearly with an increase of illumination intensity. Giant IPCE is determined by the decrease in resistivity of the bismuth oxysulfide film under illumination with photoconductivity gain, which provides the possibility of charge carriers from an external circuit to participate in the photoreduction process. Giant IPCE is observed not only in [Fe(CN)6]3− solutions, but also in electrolytes containing other photoelectron acceptors: Fe3+, I3−, quinone, H2O2. In all, solution‐processed layered bismuth oxysulfide films offer large‐area coverage, nontoxicity, low cost, and compatibility with a wide range of substrates. Abnormally high photoelectrochemical activity, as well as a band gap energy value favorable for efficient conversion of solar light (1.38 eV, direct optical transitions), proves the potential of bismuth oxysulfide photoelectrodes for a new generation of high‐performance photoconverters.
Structural and Community Change Outcomes of the Connect‐to‐Protect Coalitions: Trials and Triumphs Securing Adolescent Access to HIV Prevention, Testing, and Medical Care
Authors: Miller Robin Lin , Reed Sarah J. , Chiaramonte Danielle , Strzyzykowski Trevor , Spring Hannah , Acevedo‐Polakovich Ignacio D. , Chutuape Kate , Cooper‐Walker Bendu , Boyer Cherrie B. , Ellen Jonathan M.
Published: August 2017

Highlights

Coalition mobilization can contribute to the creation of AIDS‐competent communities.

HIV coalitions benefit from leaders who can confront political opposition to structural changes.

Coalitions can contribute to addressing the structural factors that promote HIV‐risk among youth.
Modeling and optimization of refinery hydrogen network – a new strategy to linearize power equation of new compressor
Authors: Mahmoud Ahmed , Adam Abdel Samed M. , Sunarso Jaka , Liu Shaomin
Published: August 2017

Refinery hydrogen network problem is highly nonlinear due to the equation that describes the power of new compressor. Most of the previous attempts to linearize this equation have been made by assuming constant suction and discharge pressure while taking the inlet flow rate as a variable. Such assumption may not be practical in real condition because the calculated power requirement for new compressor may not be compatible with the pressure ratio of the selected compressor. This work proposed a new linearization method for the power of new compressor that provides additional degree of freedom by allowing the solver to choose the optimum new compressor(s) that satisfied the pressure requirement of process sinks. Using our proposed model, mixed‐integer nonlinear programming (MINLP) formulation can be converted into mixed‐integer linear programming. The applicability of our model was validated using two different refinery case studies. Mixed‐integer linear programming results obtained using our model require substantially lower computational cost than their MINLP counterparts where at least 60% savings in terms of iteration number and computational processing time were achieved. The approach demonstrated here can be potentially used to approach more complex refinery hydrogen network cases where the initial guess can be obtained from the linearized MINLP problem. © 2017 Curtin University and John Wiley & Sons, Ltd.
Herpes Zoster as a Risk Factor for Incident Giant Cell Arteritis
Authors: England Bryant R. , Mikuls Ted R. , Xie Fenglong , Yang Shuo , Chen Lang , Curtis Jeffrey R.
Published: August 2017

Objective

Histopathologic studies have implicated herpes zoster (HZ) as a causative organism of giant cell arteritis (GCA). The purpose of this study was to assess the epidemiologic association of HZ events with incident GCA.

Methods

We performed a retrospective cohort study in 2 large independent US administrative data sets: Medicare 5% and Truven Health Analytics MarketScan. Eligible subjects had 12 months of continuous coverage, were >50 years old, and had no history of GCA or polymyalgia rheumatica. HZ events (complicated and uncomplicated) and GCA were identified by the presence of International Classification of Diseases, Ninth Revision, Clinical Modification codes from physician visit or hospital discharge records. Antiviral therapies and vaccinations were identified from prescription claims and drug codes. Risk of incident GCA was calculated using multivariable Cox proportional hazards regression.

Results

Among 16,686,345 subjects, a total of 5,942 GCA cases occurred, with 3.1% (MarketScan) and 6.0% (Medicare) having preceding HZ events. Unadjusted GCA incidence rates were highest in the groups with complicated and uncomplicated HZ. After multivariable adjustment, complicated HZ was associated with an increased risk of GCA (hazard ratio [HR] 1.99 [95% confidence interval (95% CI) 1.32–3.02] in the Medicare cohort and 2.16 [95% CI 1.46–3.18] in the MarketScan cohort), as was uncomplicated HZ (HR 1.42 [95% CI 1.02–1.99] and HR 1.45 [95% CI 1.05–2.01] in the respective cohorts). Vaccination and antiviral treatment were not consistently associated with GCA risk, although antiviral treatment was marginally associated with a decreased risk of GCA in the Medicare cohort (HR 0.67 [95% CI 0.46–0.99]).

Conclusion

HZ is associated with an increased risk of GCA. The infrequency of HZ in GCA patients suggests that it is only one potential trigger for GCA. Antivirals and vaccination did not consistently mitigate this risk.
Chlorination‐promoted Transformation of Isolated Pentagon Rule C78 into Fused‐pentagons‐ and Heptagons‐containing Fullerenes
Authors: Brotsman Victor A. , Ignat'eva Daria V. , Troyanov Sergey I.
Published: August 2017

Cage transformations in fullerenes are rare phenomena which are still not fully understood. We report the first skeletal transformation of an Isolated‐Pentagon‐Rule (IPR) isomer of C78 fullerene upon high‐temperature chlorination which proceeds by six‐step Stone–Wales rearrangements affording non‐IPR, non‐classical (NC) C78(NC2)Cl24 with two cage heptagons, six pairs of fused pentagons, and an unprecedented loop‐like chlorination pattern. The following loss of a C2 unit results in C76(NC3)Cl24 containing three cage heptagons.
Gender differences in safety issues during Fingolimod therapy: Evidence from a real‐life Relapsing Multiple Sclerosis cohort
Authors: Manni Alessia , Direnzo Vita , Iaffaldano Antonio , Di Lecce Valentina , Tortorella Carla , Zoccolella Stefano , Iaffaldano Pietro , Trojano Maria , Paolicelli Damiano
Published: August 2017

Objective

Benefits and risks of new therapies in Multiple Sclerosis (MS) must be balanced carefully and tailored to patients. We aimed to describe our experience with Fingolimod (FTY), correlating demographics, clinical and hematological features of the Relapsing MS (RMS) cohort with the occurring Adverse Events (AEs).

Material and Methods

Pretreatment screening tests, cardiological observation, and safety follow‐up data were analyzed in 225 RMS patients. Changes in continuous data were analyzed post hoc with Wilcoxon ranks test; categorical variables were examined using McNemar test. Two‐way repeated‐measures analysis of variance (ANOVA) was used to analyze differences between baseline characteristic of the cohorts and Liver Function Tests (LFT) alterations. Binary logistic regression models were used to identify which of the baseline factors influenced LFT alterations and the occurrence of infections.

Results

During 2 years of follow‐up 24 patients (10%) interrupted FTY. Discontinuation most often was due to AEs (n = 14) or breakthrough disease (n = 5). The most frequently AEs were infections (10.6%). After the first year patients showing an infectious episode were mostly female (p = .04). The infections did not correlate with the decrease in white blood cells or to lymphocyte count. AST and ALT alterations ​​were observed mostly in males (p = .002 and p = .01, respectively), and increase in GGT ​​was reported in subjects older at FTY beginning (p < .05).

Conclusions

For a patient‐centered safety monitoring of FTY, we may apply gender‐specific warnings, for the detection of transaminases abnormalities and infectious episodes.
Wnt5a regulates the cell proliferation and adipogenesis via MAPK‐independent pathway in early stage of obesity
Authors: Tang Qi , Chen Chang , Zhang Yan , Dai Minjia , Jiang Yichen , Wang Hang , Yu Mei , Jing Wei , Tian Weidong
Published: August 2017

The early stage of obesity is an important stage in the development of obesity. However, there are few studies which explored the property or changes in obesity at early stage especially involving Wnt5a. The associated gene expression of Wnt5a on cell regeneration and the effect of Wnt5a on rat adipose‐derived stem cell (rASC) proliferation and adipogenesis need additional study. Here, we investigated the changes in obesity at early stage and how Wnt5a regulates rASC regeneration, proliferation, and adipogenesis. Our data revealed that obesity at early stage measured by Lee index presented a state with impaired adipogenesis and more infiltrated inflammatory cells but without significant changes in adipocyte sizes and inflammatory factors. The process might be associated with anti‐canonical Wnt pathway and a reciprocal Wnt5a/JNK pathway. Besides the gene expression of Wnt5a decreased from cell passage 1 to passage 3. The cell proliferation was regulated by increasing dose of Wnt5a with the maximal effect at 50 ng/mL and 50 ng/mL Wnt5a suppressed adipogenic differentiation at middle‐late stage of adipogenesis via anti‐β‐catenin and a mitogen‐activated protein kinase (MAPK) signaling‐independent manner. Accordingly, the research helps to gain further insights into the early stage of obesity and its associated changes on a cellular and molecular level.
Comparative study of hematopoietic stem and progenitor cells between sexes in mice under physiological conditions along time
Authors: Gasco Samanta , Rando Amaya , Zaragoza Pilar , García‐Redondo Alberto , Calvo Ana Cristina , Osta Rosario
Published: August 2017

Hematopoietic stem and progenitor cells (HSPCs) are attractive targets in regenerative medicine, although the differences in their homeostatic maintenance between sexes along time are still under debate. We accurately monitored hematopoietic stem cells (HSCs), common lymphoid progenitors (CLPs), and common myeloid progenitors (CMPs) frequencies by flow cytometry, by performing serial peripheral blood extractions from male and female B6SJL wild‐type mice and found no significant differences. Only modest differences were found in the gene expression profile of Slamf1 and Gata2. Our findings suggest that both sexes could be used indistinctly to perform descriptive studies in the murine hematopoietic system, especially for flow cytometry studies in peripheral blood. This would allow diminishing the number of animals needed for the experimental procedures. In addition, the use of serial extractions in the same animals drastically decreases the number of animals needed.
Oxygen‐Rich Carbon Quantum Dots as Catalysts for Selective Oxidation of Amines and Alcohols
Authors: Ye Jianglin , Ni Kun , Liu Jie , Chen Guanxiong , Ikram Mujtaba , Zhu Yanwu
Published: August 2017

Metal‐free carbocatalysis has been widely utilized for aerobic oxidative reactions. Here, we report that oxygen‐rich carbon quantum dots (O‐CQDs) demonstrate a catalytic performance superior to graphene oxide, if used as a metal‐free nanocatalyst for the direct transformation of amines and alcohols, under mild and solvent‐free conditions. O‐CQDs show a yield of 75 % for the oxidative coupling of amine to imine (with 5 wt % catalyst loading) and a conversion of 3.8 % for benzyl alcohol (with 2 wt % catalyst loading). The catalytic activities of thermally treated O‐CQDs are further improved for benzylamine, for example, indicated by a yield of up to 98 % with 4 wt % catalyst loading. In addition, O‐CQDs show a photoenhanced catalytic ability of amine (98 % yield with 5 wt % catalyst loading for 6 h reaction). Characterizations and simulations show that numerous carboxyl oxygen functional groups and unpaired electrons at the edge sites of O‐CQDs are likely involved in the aerobic oxidation of amines.
Semirational Engineering of the Naphthalene Dioxygenase from Pseudomonas sp. NCIB 9816‐4 towards Selective Asymmetric Dihydroxylation
Authors: Halder Julia M. , Nestl Bettina M. , Hauer Bernhard
Published: August 2017

Enzyme‐catalyzed asymmetric dihydroxylation is a powerful tool for the selective oxyfunctionalization of various organic compounds. By applying Rieske non‐heme dioxygenases (ROs), molecular oxygen and a reduction equivalent are needed for the generation of vicinal cis‐diols. We report a comprehensive mutagenesis study of the active site of the naphthalene dioxygenase from Pseudomonas sp. NCIB 9816‐4 comprising 62 variants. We aimed to understand the important structure–function relationships by investigating different substituted arene substrates and the geometry of the active site. Introducing single‐point mutations at positions F202, A206, V260, H295, F352, and L307 resulted in drastic shifts in the reaction specificity, regioselectivity, and stereoselectivity (≥90 %) while maintaining the residual activity towards the natural substrate naphthalene.
Functional‐Polymer Library through Post‐Polymerization Modification of Copolymers Having Oleate and Pentafluorophenyl Pendants
Authors: Maiti Binoy , Haldar Ujjal , Rajasekhar Tota , De Priyadarsi
Published: August 2017

Poly[2‐(methacryloyloxy)ethyl oleate‐co‐pentafluorophenyl methacrylate] [P(MAEO‐co‐PFPMA)] random copolymers with oleate and pentafluorophenyl side‐chain pendants were synthesized. These copolymers were utilized as dual‐reactive polymeric scaffolds in a range of post‐polymerization modification strategies involving thiol‐ene and para‐fluoro‐thiol substitution, amidation, trans‐esterification, and epoxidation followed by amidation. The 2‐(methacryloyloxy)ethyl oleate (MAEO) functional handle in the copolymer is open to functionalization at its internal double bond through thermally initiated thiol‐ene reaction, whereas the pentafluorophenyl moiety of the pentafluorophenyl methacrylate (PFPMA) unit undergoes para‐fluoro‐thiol substitution under basic conditions at room temperature. By means of these modification approaches, the P(MAEO‐co‐PFPMA) copolymer was orthogonally ligated with thiol compounds having, for example, alkyl, hydroxyl, and protected amine functional groups. Furthermore, different functional groups such as benzyl, allyl, methacrylate, pyrene, and water‐soluble poly(ethylene glycol) were easily introduced into the side chain of the P(MAEO‐co‐PFPMA) copolymer by amidation, trans‐esterification, and epoxidation followed by amidation. Functionalization of both the reactive pendants with the various organic substituents was confirmed by 1H and 19F NMR spectroscopy, gel permeation chromatography, and fluorescence spectroscopy.
Electrostatic Modification for Promotion of Flavin‐Mediated Oxidation of a Probe for Flavin Detection
Authors: Lee Dong‐Nam , Bae Sohyeon , Han Kyungja , Shin Ik‐Soo , Kim Seong Keun , Hong Jong‐In
Published: August 2017

Electrostatic effects on the redox photochemistry of synthetic probes (1, 2, and 1–Zn) are examined by adjusting the thermodynamic driving force of their oxidation reactions. The redox photochemistry was simply controlled by introducing a zinc binding site (2,2′‐dipicolylamine (DPA)) on the coumarin moiety of probe 2. Zinc complexation produced a positively charged environment on the coumarin (1–Zn), which lowered the electron density of a nearby 9 H‐xanthene ring, attenuating the auto‐oxidation of 1–Zn by 45 % compared with that of probe 1 at 298 K. The positive net charge of 1–Zn also provided an attractive Coulombic force toward the phosphate of flavin mononucleotide and flavin adenine dinucleotide, which lowered the reduction potential of the electron acceptor (isoalloxazine) and improved intermolecular electron transfer from the 9 H‐xanthene ring to isoalloxazine. The flavin‐mediated oxidation rate of 1–Zn was increased to 1.5 times that of probe 2. Probe 1–Zn showed highly selective sensing behaviour toward flavins, producing an intense brightness (ϵΦF=2.80×103 m−1 cm−1) in the long‐wavelength regions (λmax=588 nm) upon flavin‐mediated oxidation. Furthermore, probes 1–Zn and 2 were successfully applied to eosinophil imaging and the differential diagnosis of eosinophilia; this demonstrates their use as diagnostic tools.
Novel Ni‐Ga alloy based catalyst for converting CO2 to methanol
Authors: Nguyen Hong Khanh Dieu , Dang Toan Hong , Nguyen Nga Le To , Nguyen Ha Thi , Dinh Ngo Thi
Published: August 2017

Novel and advanced catalysts based on Ni‐Ga alloy were prepared through co‐condensation method with and without evaporation of water solvent for converting CO2 to methanol. The co‐condensations used Ni(NO3)2 and Ga metal as beginning precursors under alkaline media. Various Ni/Ga molar ratios and temperature of the co‐condensation‐evaporation method were investigated in order to obtain Ni5Ga3 alloy composition as active phase for the catalysts. The results confirmed that the stoichiometry of 5/3 could be reached at the same molar ratio of the beginning precursors, and the suitable temperature of the method was 80 °C for a certain time of 24 h. The Ni‐Ga based catalyst activity and selectivity were also tested in the conversion of CO2 to methanol at atmospheric pressure and 220 °C for different periods of time. The results showed that the catalyst was an excellent candidate for this process compared to other catalysts when exposing good selectivity over 90 % during long periods of time. Many techniques were used including X‐Ray Diffraction (XRD), Thermogravimetric Analysis (TGA), X‐Ray Photoelectron Spectroscopy (XPS), Nitrogen Adsorption–Desorption Analysis (BET), and Gas Chromatography (GC) to characterize the catalyst structure and the reaction performance, respectively.
Computational fluid dynamic model for the estimation of coke formation and gas generation inside petrochemical furnace pipes with the use of a kinetic net
Authors: Valus Maria Gorete , Fontoura Diener Volpin Ribeiro , Serfaty Ricardo , Nunhez José Roberto
Published: August 2017

Petrochemical furnaces are used in the petrochemical industry for the preheating of crude oil, residue, gasoil, naphtha, kerosene, and diesel through refining operations. When the fluid flows inside the furnace pipes, thermal cracking occurs. During the heating process, a generation of lighter fractions of petroleum and coke formation takes place. Coke adheres to the wall of the pipes, increasing pressure drop and internally insulating the pipes. Consequently, heat transfer is affected. In most of these processes, during heating and thermal cracking, gases are generated, forming a liquid‐gas two‐phase flow in the pipe. In this work, thermal cracking and gas generation are represented by a kinetic net which takes into account the constituent fractions of the petroleum load, which are represented by six pseudo‐components. The CFD model was able to predict the lighter petroleum fractions and the gas generation as well as the coke formation inside the tube. Coke concentration increases along the pipe as the average temperature of the mixture increases.
Thermophysical properties of dimethyl ether/Athabasca bitumen system
Authors: Haddadnia Ali , Azinfar Bahareh , Zirrahi Mohsen , Hassanzadeh Hassan , Abedi Jalal
Published: August 2017

Solvent‐aided thermal recovery processes have recently gained practical and research interests among other thermal recovery methods due to their reduced environmental footprint and superior energy efficiency. One of the main challenges in design of solvent‐based methods is selection of an appropriate solvent that maximizes the bitumen and solvent recoveries. This study attempts to introduce dimethyl ether (DME) as a non‐conventional solvent for heavy oil and bitumen recovery. To investigate the performance of the proposed solvent, thermophysical properties of DME/bitumen are studied. Vapour‐liquid equilibrium measurements including solubility, density, and viscosity are performed at three temperatures (100, 125, and 150 °C) and pressures up to 6 MPa. The results were compared with propane/bitumen and butane/bitumen systems. All the measured properties fall between propane and butane systems. The solubility and density data were fairly represented using PR‐EoS with AARDs of 10.3 and 1.43 %, respectively, and viscosity data were correlated applying the Pederson corresponding state model with an AARD of 10.7 %. The results suggest that DME is a suitable substitute for solvents such as propane and butane in solvent‐aided thermal recovery of bitumen from oil sands.
Load balanced transaction scheduling using Honey Bee Optimization considering performability in on‐demand computing system
Authors: Mahato Dharmendra Prasad , Singh Ravi Shankar
Published: August 2017

The scheduling of load balanced transactions is an emerging problem in on‐demand computing system. This problem can be studied considering several parameters such as resource availability, performance, and reliability. The existing approaches to find the exact solutions for this problem are limited. This paper presents a Honey Bee Optimization (HBO)–based method to solve the mentioned problem. In this method, first, the load of the system is balanced and then the transactions are scheduled using foraging behavior of honey bees to find the optimal solutions. We also modify four known scheduling algorithms such as Ant Colony Optimization (ACO), Hierarchical Load Balanced Algorithm (HLBA), Dynamic and Decentralized Load Balancing (DLB), and Randomized to obtain transaction scheduling algorithms for the purpose of comparison with our proposed algorithm. The compared results show that the proposed algorithm performs better than the modified existing algorithms.
Reducing EMF exposure from WSNs using transmission scheduling
Authors: Dragomir Dan
Published: August 2017

There is increasing pressure from the public to study the effects of electromagnetic field exposure and reduce this exposure for future networks or, at the least, keep it at a constant level. According to the World Health Organization, no link has been found between low levels of exposure to radio waves (as emitted by WiFi devices or mobile phones) and adverse health effects, but reducing exposure has other benefits besides public acceptance, such as reduced interference and improved network performance. Wireless sensor networks (WSNs) have rarely been studied from an exposure point of view, but their continuing expansion as part of the new Internet of Things vision is slowly bringing them to the spotlight. This work presents a novel evaluation of WSN emissions, using the Exposure Index proposed by the Low EMF Exposure Future Networks (LEXNET) project. Together with this evaluation, a method of reducing exposure by intelligently scheduling WSN transmissions is also proposed. The scheduling method is evaluated using a proposed scenario (compatible with evaluations of other technologies performed in LEXNET) both from a theoretical perspective and in a practical implementation, and results are compared with a baseline solution. Copyright © 2017 John Wiley & Sons, Ltd.
Simultaneous Occurrence of Quadruple Lewis Acid–Base Interactions between Selenium Atoms in Selenocarbonyl Dimers
Authors: Buralli Gabriel J. , Duarte Darío J. R. , Peruchena Nélida M. , Alkorta Ibon
Published: August 2017

High‐level quantum chemical calculations are performed to investigate C=Se⋅⋅⋅Se=C interactions. Bounded structures are found with binding energies between −4 and −7 kJ mol−1. An energy decomposition analysis shows that dispersion is the more attractive term, and in all cases save one, the electrostatic interaction is attractive despite each selenium atom having a positive σ‐hole at the extension of the C=Se bond. The topological analysis of the molecular electrostatic potential andL(r)=−∇2ρ(r) function, and natural bond orbital analysis reveal that these particular Se⋅⋅⋅Se contacts can be considered to be quadruple Lewis acid–base interactions.
CO2 Activation over Catalytic Surfaces
Authors: Álvarez Andrea , Borges Marta , Corral‐Pérez Juan José , Olcina Joan Giner , Hu Lingjun , Cornu Damien , Huang Rui , Stoian Dragos , Urakawa Atsushi
Published: August 2017

This article describes the main strategies to activate and convert carbon dioxide (CO2) into valuable chemicals over catalytic surfaces. Coherent elements such as common intermediates are identified in the different strategies and concisely discussed based on the reactivity of CO2 with the aim to understand the decisive factors for selective and efficient CO2 conversion.
LCST Phase Behavior and Complexation with Water of an Ionic Liquid Incorporating the 5‐Phenyltetrazolate Anion
Authors: Moura Leila , Brown Lucy C. , Blesic Marijana , Holbrey John D.
Published: August 2017

The use of 5‐phenyltetrazole, a bioisostere of benzoic acid, as an anion source to prepare an ionic liquid is described for the first time. Tetrabutylphosphonium 5‐phenyltetrazolate undergoes phase separation from water with lower critical solution temperature phase behavior, in contrast to completely water miscible tetrabutylphosphonium benzoate, and also exhibits strong complexation with water with both eutectic and peritectic behavior that has not previously been observed in ionic liquid+water systems. The anhydrous and trihydrate salts were isolated and characterized by single crystal X‐ray diffraction.
Addressing Pharmaceutical Injuries: The US Landscape
Authors: Bakker Cecilia , Honig Nicholaas
Published: August 2017

The legal landscape for addressing an injury related to the use of a pharmaceutical product varies from country to country. Approximately 10 countries have adopted some form of no‐fault compensation, in which an individual must establish that they sustained an injury caused by the medicine, but need not demonstrate that the manufacturer acted negligently in order to recover. This commentary compares and contrasts the approach taken in Japan with that in the United States.
Design and Evaluation of a Boron Dipyrrin Electrophore for Redox Flow Batteries
Authors: Heiland Niklas , Cidarér Clemens , Rohr Camilla , Piescheck Mathias , Ahrens Johannes , Bröring Martin , Schröder Uwe
Published: August 2017

A boron dipyrrin (BODIPY) dye was designed as a molecular single‐component electrophore for redox flow batteries. All positions of the BODIPY core were assessed on the basis of literature data, in particular cyclic voltammetry and density functional calculations, and a minimum required substitution pattern was designed to provide solubility, aggregation, radical cation and anion stabilities, a large potential window, and synthetic accessibility. In‐depth electrochemical and physical studies of this electrophore revealed suitable cathodic behavior and stability of the radical anion but rapid anodic decomposition of the radical cation. The three products that formed under the conditions of controlled oxidative electrolysis were isolated, and their structures were determined by spectroscopy and comparison with a synthetic model compound. From these structures, a benzylic radical reactivity, initiated by one‐electron oxidation, was concluded to play the major role in this unexpected decomposition.
Recent advances in analytical methods for the therapeutic drug monitoring of immunosuppressive drugs
Authors: Zhang Yu , Zhang Rui
Published: August 2017

Therapeutic drug monitoring (TDM) of immunosuppressive drugs (ISDs) with a narrow therapeutic index is an increasingly popular tool for minimizing drug toxicity while maximizing the prevention of graft loss and organ rejection. This review focuses on trends regarding analytical methods for the TDM of ISDs since 2011. The five most commonly prescribed immunosuppressive medications are critically reviewed: cyclosporine A, tacrolimus, sirolimus (rapamycin), everolimus, and mycophenolic acid. This review introduces the general background of TDM and ISDs and presents the recent developments in using liquid chromatography–tandem mass spectrometry (LC–MS/MS) and immunoassays for the TDM of ISDs. Finally, a future perspective for these analytical methods is briefly discussed.
MDA, MDMA, and other “mescaline‐like” substances in the US military's search for a truth drug (1940s to 1960s)
Authors: Passie Torsten , Benzenhöfer Udo
Published: August 2017

This article describes the context in which 3,4‐methylenedioxyamphetamine (MDA), 3,4‐methylenedioxymethamphetamine (MDMA) and other mescaline‐like compounds were explored as hallucinogens for military and intelligence purposes from the 1940s to the 1960s. Germans first tested mescaline as a “truth drug” in a military context. In the 1940s, the United States military started testing hallucinogenic substances as truth drugs for interrogation and behavior manipulation. After tests carried out using mescaline and other drugs in 1950, some derivatives of mescaline were synthesized by the Army for the exploration of possible “speech‐inducing” effects. After insufficient animal testing, the substances were given to patients at the New York State Psychiatric Institute (NYSPI). 3,4‐Methylenedioxy‐N‐ethylamphetamine (MDE), a compound almost identical to MDMA, was among the compounds delivered for testing at the NYSPI. During tests with other derivatives (3,4‐dimethoxyphenethylamine (DMA), 3,4‐methylenedioxyphenethylamine (MDPEA), MDA) in 1952–53, an unwitting patient died in these tests, which was kept secret from the public. Research was interrupted and toxicological animal testing procedures were initiated. The secret animal studies run in 1953/1954 revealed that some of the “mescaline derivatives” tested (e.g. MDA, MDE, DMA, 3,4,5‐trimethoxyamphetamine (TMA), MDMA) were considered for further testing in humans. In 1955, the military changed focus to lysergic acid diethylamide (LSD), but some interest in mescaline‐like compounds remained for their ability to change mood and habit without interfering with cognition and sensory perception. Based on the known documents, it remains unclear (but probable) whether any of the mescaline derivatives tested were being used operationally.
Expression of genes and proteins of the pax‐six‐eya‐dach network in the metamorphic sea urchin: Insights into development of the enigmatic echinoderm body plan and sensory structures
Authors: Byrne Maria , Koop Demian , Morris Valerie B. , Chui Juanita , Wray Gregory A. , Cisternas Paula
Published: August 2017

Background: Photoreception‐associated genes of the Pax‐Six‐Eya‐Dach network (PSEDN) are deployed for many roles in addition to photoreception development. In this first study of PSEDN genes during development of the pentameral body in sea urchins, we investigated their spatial expression in Heliocidaris erythrogramma. Results: Expression of PSEDN genes in the hydrocoele of early (Dach, Eya, Six1/2) and/or late (Pax6, Six3/6) larvae, and the five hydrocoele lobes, the first morphological expression of pentamery, supports a role in body plan development. Pax6, Six1/2, and Six3/6 were localized to the primary and/or secondary podia and putative sensory/neuronal cells. Six1/2 and Six3/6 were expressed in the neuropil region in the terminal disc of the podia. Dach was localized to spines. Sequential up‐regulation of gene expression as new podia and spines formed was evident. Rhabdomeric opsin and pax6 protein were localized to cells in the primary podia and spines. Conclusions: Our results support roles for PSEDN genes in development of the pentameral body plan, contributing to our understanding of how the most unusual body plan in the Bilateria may have evolved. Development of sensory cells within the Pax‐Six expression field is consistent with the role of these genes in sensory cell development in diverse species. Developmental Dynamics 247:239–249, 2018. © 2017 Wiley Periodicals, Inc.