bluuebunny/crossref_metadata_2025 huggingface dataset:
Breeding phenology and performance for four swallows over 57 years: relationships with temperature and precipitation
Authors: Imlay Tara L. , Mills Flemming Joanna , Saldanha Sarah , Wheelwright Nathaniel T. , Leonard Marty L.
Published: April 2018

Climate change can drive population declines for many species, often through changes to their food supply. These changes can involve a mis‐timing between periods of high food demand and peak food availability, typically from advances in breeding phenology, and/or an overall reduction in food availability. Aerial insectivores, birds that feed on insects caught in flight, are experiencing steep population declines possibly because of shifts in the timing and/or abundance of aerial insects. We determined whether changes in breeding performance over time could account for declines in Bank Riparia riparia, Barn Hirundo rustica, Cliff Petrochelidon pyrrhonota, and Tree Tachycineta bicolor Swallows, and if so, whether changes were related to shifts in breeding phenology and/or climate change. We compared breeding performance and phenology in Maritime Canada before (1962–1972) and after (2006–2016) the onset of steep population declines during the mid‐1980s, to determine whether breeding performance was reduced or phenology was advanced. Then, we modeled relationships between temperature, precipitation, breeding phenology, and performance for Barn and Tree Swallows, the only species with sufficient data, from 1960 to 2016, to determine whether phenology and performance were related to climatic conditions. Between the two time periods, we found significantly lower performance in Bank Swallows, higher performance in Barn and Tree Swallows, and unchanged performance in Cliff Swallows. We also found clutch initiation dates advanced by 8–10 d for all species except Bank Swallows. On the breeding grounds, warmer winter temperatures for Tree Swallows and less winter precipitation for Barn and Tree Swallows in a given year were associated with earlier breeding, and for Tree Swallows, changes in nestling survival. Otherwise, Barn and Tree Swallow breeding performance was unaffected by winter temperature and precipitation. Our results suggest that in this region poorer breeding performance could contribute to population declines for Bank Swallows but not for the other three species.
Patch size, isolation, and matrix effects on biodiversity and ecosystem functioning in a landscape microcosm
Authors: Spiesman Brian J. , Stapper Andres P. , Inouye Brian D.
Published: April 2018

The amount and arrangement of habitat is a fundamental determinant of biodiversity and ecosystem processes in a landscape. Biodiversity is expected to decline following habitat loss and isolation, potentially impeding ecosystem function. But because greater isolation usually accompanies habitat loss, the effects of habitat amount and isolation can be confounded. Moreover, the type or quality of the intervening matrix habitat can mediate amount and isolation effects on biodiversity. We used a landscape microcosm of oak leaf litter patches to examine the responses of bacterial communities and the ecosystem function of oak leaf decomposition to patch size, degree of isolation, and matrix habitat type (pine litter or bare ground). We found that oak patch size had no significant effect on bacterial communities or decomposition rates. However, bacterial richness increased with greater patch isolation and when oak litter patches were surrounded by a matrix of pine litter, rather than bare ground. The benefit of patch isolation for biodiversity runs counter to that expected by island biogeography theory, suggesting that spatially dependent interspecific interactions, such as predation or competition, may override direct dispersal effects. Higher bacterial richness in oak litter patches surrounded by a pine litter matrix indicated that spillover from neighboring matrix habitat can increase local richness. Instead of greater bacterial richness enhancing ecosystem functioning, leaf litter decomposition was negatively correlated with bacterial richness: Decomposition was slower in isolated oak litter patches and patches surrounded by a pine litter matrix. This negative relationship may be a result of spatial dynamics that can promote the persistence of bacteria from pine litter habitats that are not well suited to oak litter decomposition. Overall, our experiment indicates that effects of habitat loss, isolation, and matrix quality on richness and composition may depend on spatially constrained interspecific interactions, which can determine the functional ability of communities.
Fire regimes approaching historic norms reduce wildfire‐facilitated conversion from forest to non‐forest
Authors: Walker Ryan B. , Coop Jonathan D. , Parks Sean A. , Trader Laura
Published: April 2018

Extensive high‐severity wildfires have driven major losses of ponderosa pine and mixed‐conifer forests in the southwestern United States, in some settings catalyzing enduring conversions to non‐forested vegetation types. Management interventions to reduce the probability of stand‐replacing wildfire have included mechanical fuel treatments, prescribed fire, and wildfire managed for resource benefit. In 2011, the Las Conchas fire in northern New Mexico burned forested areas not exposed to fire for >100 yr, but also reburned numerous prescribed fire units and/or areas previously burned by wildfire. At some sites, the combination of recent prescribed fire and wildfire approximated known pre‐settlement fire frequency, with two or three exposures to fire between 1977 and 2007. We analyzed gridded remotely sensed burn severity data (differenced normalized burn ratio), pre‐ and post‐fire field vegetation samples, and pre‐ and post‐fire measures of surface fuels to assess relationships and interactions between prescribed fire, prior wildfire, fuels, subsequent burn severity, and patterns of post‐fire forest retention vs. conversion to non‐forest. We found that Las Conchas burn severity was lowest, and tree survival was highest, in sites that had experienced both prescribed fire and prior wildfire. Sites that had experienced only prescribed or prior wildfire exhibited moderate burn severity and intermediate levels of forest retention. Sites lacking any recent prior fire burned at the highest severity and were overwhelmingly converted to non‐forested vegetation including grassland, oak scrub, and weedy, herbaceous‐dominated types. Burn severity in the Las Conchas fire was closely linked to surface woody fuel loads, which were reduced by prior wildfire and prescribed fire. Our results support the restoration of fire regimes via prescribed fire and resource benefit wildfire to promote the resiliency of forest types vulnerable to fire‐mediated type conversion. The application of prescribed fire to reduce surface fuels following wildfire may reduce forest loss during subsequent fire under more extreme conditions. These findings are especially relevant given likely increases in vulnerability associated with climate change impacts to wildfire and forest dynamics.
Quantifying forest carbon dynamics as a function of tree species composition and management under projected climate
Authors: Swanteson‐Franz Rachel J. , Krofcheck Daniel J. , Hurteau Matthew D.
Published: April 2018

Uncertainty remains about whether current rates of forest carbon uptake will be maintained with on‐going climate change and increasing rates of disturbance. The potential exists for climate and disturbance to exceed the physiological tolerances of certain tree species and push forest ecosystems to a point where they become C sources. Thus, a diversity of tree species with a range of physiological tolerances could provide adaptive capacity and potentially sustain a C sink despite adverse abiotic influences. The fire‐prone pine forests of the southeasternUSAhave been impacted by a combination of land use and fire exclusion, which has altered the demographics and composition of these historically diverse forests. We sought to quantify how prescribed fire and planting of climate‐resilient tree species would alter forest carbon dynamics under projected climate change at Fort Benning, Georgia. This landscape is comprised of a diversity of forest types with a range of land‐use histories and is heavily managed to meet military training objectives and federally listed species habitat requirements. We used a simulation approach to determine species‐specific growth responses to projected climate and develop two management scenarios: no‐management and prescribed fire coupled with planting. We ran landscape simulations of these two management scenarios under climate projections from ten global climate models to quantify how active management would alter forest carbon dynamics as a function of changing climate and wildfire. We found that the prescribed fire and plant scenario increased total ecosystem carbon (TEC) over our no‐management scenario by over 20 Mg C/m2by late century. Despite the differences inTEC, differences in net ecosystem exchange were not realized over the entire simulation. The primary drivers ofTECdifferences were sustained carbon uptake and lower carbon loss to wildfire in the prescribed fire and plant scenario. Our results demonstrate that under projected climate, managing to reduce the impacts of fire and planting climate‐adapted species can increase the mitigation potential of these forests.
Approximate Synthesis of a Higher‐Order Passive Complex Coefficient Filter Using Autotransformers
Authors: YAMOTO DAIKI , SHOUNO KAZUHIRO
Published: April 2018

In this paper, a new method for synthesizing a higher‐order passive complex filter using autotransformers is proposed. The proposed filter can be synthesized approximately by transforming the conventional one. Since the proposed transformation replaces all transformers with autotransformers, the proposed filter has no floating windings. As examples, both first‐order and third‐order complex filters are synthesized. The validity of the proposed method was confirmed through computer simulation and experiment. Due to approximate synthesis, the transfer function of the real output is different from that of the imaginary output. However, both of them have roughly the same response near the passband. Experimental results show good agreement with the theoretical value. It means that the proposed method is valid for the practical application.
Motion Planning by T‐RRT with Potential Function for Vertical Articulated Robots
Authors: KABUTAN RYO , NISHIDA TAKESHI
Published: April 2018

RRT (rapidly exploring random tree) with random sampling is an effective method for path planning, and is often used for robot manipulators. The RRT has many modified methods for applying various problems and conditions. Particularly, T‐RRT (Transition‐based RRT) one of those has advantage that it is able to adopt arbitrary evaluation function. In this paper, a novel path planning method based on the T‐RRT is proposed for ensuring “quality” of a generated path. Then, its effectiveness is evaluated via comparison with other sampling‐based methods using simulation of the industrial robot having seven DOFs.
HT‐NbOsB: Experimental and Theoretical Investigations of a Boride Structure Type Containing Boron Chains and Isolated Boron Atoms
Authors: Forsythe Ryland , Scheifers Jan P. , Zhang Yuemei , Fokwa Boniface P. T.
Published: April 2018

The new ternary compound Nb1–xOs1+xB (x = 0.17) was synthesized by arc‐melting of the elements in a water‐cooled crucible under an argon atmosphere and was characterized by powder and single‐crystal X‐ray diffraction as well as energy‐dispersive X‐ray spectroscopy (EDX). The compound crystallizes with a new orthorhombic structure type in the space group Pnma (no. 62) with the lattice parameters a = 11.283(2) Å, b = 3.0101(4) Å, and c = 12.883(2) Å. The structure contains isolated boron atoms in osmium trigonal prisms, and boron chains in face‐sharing niobium trigonal prisms. Electronic structure relaxation has confirmed the crystallographic parameters, and crystal orbital Hamilton population (COHP) bonding analysis was used to understand the chemical bonding. It is shown that a local stabilizing effect from replacing Nb with Os is favored despite a global destabilization.
Effect profile of paracetamol, Δ9‐THC and promethazine using an evoked pain test battery in healthy subjects
Authors: van Amerongen G. , Siebenga P. , de Kam M.L. , Hay J.L. , Groeneveld G.J.
Published: April 2018

Background

A battery of evoked pain tasks (PainCart) was developed to investigate the pharmacodynamic properties of novel analgesics in early‐phase clinical research. As part of its clinical validation, compounds with different pharmacological mechanisms of actions are investigated. The aim was to investigate the analgesic effects of classic and nonclassic analgesics compared to a sedating negative control in a randomized placebo‐controlled crossover study in 24 healthy volunteers using the PainCart.

Methods

The PainCart consisted of pain tasks eliciting electrical, pressure, heat, cold and inflammatory pain. Subjective scales for cognitive functioning and psychotomimetic effects were included. Subjects were administered each of the following oral treatments: paracetamol (1000 mg), Δ9‐THC (10 mg), promethazine (50 mg) or matching placebo. Pharmacodynamic measurements were performed at baseline and repeated up to 10 h postdose.

Results

Paracetamol did not show a significant reduction in pain sensation or subjective cognitive functioning compared to placebo. Promethazine induced a statistically significant reduction in PTT for cold pressor and pressure stimulation. Furthermore, reduced subjective alertness was observed. Δ9‐THC showed a statistically significant decrease in PTT for electrical and pressure stimulation. Δ9‐THC also demonstrated subjective effects, including changes in alertness and calmness, as well as feeling high and psychotomimetic effects.

Conclusions

This study found a decreased pain tolerance due to Δ9‐THC and promethazine, or lack thereof, using an evoked pain task battery. Pain thresholds following paracetamol administration remained unchanged, which may be due to insufficient statistical power. We showed that pain thresholds determined using this pain test battery are not driven by sedation.

Significance

The multimodal battery of evoked pain tasks utilized in this study may play an important role in early‐phase clinical drug development. This battery of pain tasks is not sensitive to the effects of sedation alone, and thus suitable to investigate the analgesic potential of novel analgesic compounds.
The Multidimensional Symptom Index: A new patient‐reported outcome for pain phenotyping, prognosis and treatment decisions
Authors: Walton D.M. , Marsh J.
Published: April 2018

Background

There are few patient‐reported outcomes routinely used that capture frequency and interference of different pain‐related symptoms on a single scale. The purpose of this study was to describe the development and initial validation of the new Multidimensional Symptom Index (MSI).

Methods

Items were generated from patient interviews of the experience of chronic pain. Health valuations were created from rankings of 82 healthy subjects for each of 120 symptom (×10) × frequency (×3) × interference (×4) combinations using preference‐based health valuations (0–100). Ranks for each symptom combination were then used in scale scoring. A sample of 300 patients with acute or chronic pain subsequently completed the MSI and a battery of other tools. Exploratory (EFA) and Confirmatory (CFA) factor analyses were triangulated with theory to arrive at the factor structure. Convergent validity was tested against established measures.

Results

Health rankings resulted in scores of 0–12 for each of the 10 symptom types. Factor analyses revealed two factors: MSI Somatic Symptoms and MSI Non‐Somatic Symptoms. The MSI also quantified number of symptoms experienced (/10), mean frequency (/3) and mean interference (/4). The indices showed appropriate associations with the established PROs.

Conclusions

The MSI is a new symptom‐focused PRO that allows patient phenotyping and may have value for screening, prognosis and evaluating change.

Significance

This article presents the development and psychometric properties of a new measure of pain and related symptom frequency and interference. This measure could aid clinicians in establishing clinically relevant pain phenotypes for screening, prognosis and treatment decisions.
Simultaneous Determination of Homovanillic and Vanillylmandelic Acid by HPLC Using a Coulometric Detector with Renewable Glassy Carbon Microbeads Based Working Electrode
Authors: Mika Jan , Barek Jiří , Zima Jiří , Moreira Josino Costa , Dejmková Hana
Published: April 2018

Homovanilic (HVA) and vanillylmandelic (VMA) acid are catecholamines metabolites commonly used as cancer biomarkers. New method for simultaneous determination of both these metabolites is presented, using recently developed flow‐through coulometric detector based on glassy carbon microbeads. This application presents the potential opportunities of the above mentioned coulometric detector for the simultaneous determination of mixture of substances in complicated matrix in combination with gradient chromatography. Optimum conditions were set as follows: mobile phase consisting of acetonitrile (eluent A) and ten time diluted B‐R buffer pH 3 (eluent B) with gradient program 5 % A (2 min), 5 % A to 25 % A (8 min), 25 % A (4 min), 25 % A to 95 % A (1 min), and 95 % A (4 min); flow rate of mobile phase 0.7 mL min−1, detection potential +1.3 V, and injection volume 20 μL. Calibration dependences of both metabolites were linear from concentration 100 μmol L−1 to their quantitation limits (i.e. 0.6 μmol L−1 for HVA and 1.3 μmol L−1 for VMA, respectively). Standard addition method was applied for the determination of these analytes in human urine. Obtained results are in agreement with results of HPLC method with UV detector.
Low and high prices can improve covariance forecasts: The evidence based on currency rates
Authors: Fiszeder Piotr
Published: April 2018

In this paper we introduce a new specification of the BEKK model, where its parameters are estimated with the use of closing and additionally low and high prices. In an empirical application, we show that the use of additional information related to low and high prices in the formulation of the BEKK model improved the estimation of the covariance matrix of returns and increased the accuracy of covariance and variance forecasts based on this model, compared with using closing prices only. This analysis was performed for the following three most heavily traded currency pairs in the Forex market: EUR/USD, USD/JPY, and GBP/USD. The main result obtained in this study is robust to the applied forecast evaluation criterion. This issue is important from a practical viewpoint, because daily low and high prices are available with closing prices for most financial series.
Brain PET substrate of impulse control disorders in Parkinson's disease: A metabolic connectivity study
Authors: Verger Antoine , Klesse Elsa , Chawki Mohammad B. , Witjas Tatiana , Azulay Jean‐Philippe , Eusebio Alexandre , Guedj Eric
Published: April 2018

Impulse control disorders (ICDs) have received increased attention in Parkinson's disease (PD) because of potentially dramatic consequences. Their physiopathology, however, remains incompletely understood. An overstimulation of the mesocorticolimbic system has been reported, while a larger network has recently been suggested. The aim of this study is to specifically describe the metabolic PET substrate and related connectivity changes in PD patients with ICDs. Eighteen PD patients with ICDs and 18 PD patients without ICDs were evaluated using cerebral 18F‐fluorodeoxyglucose positron emission tomography. SPM‐T maps comparisons were performed between groups and metabolic connectivity was evaluated by interregional correlation analysis (IRCA; p < .005, uncorrected; k > 130) and by graph theory (p < .05). PD patients with ICDs had relative increased metabolism in the right middle and inferior temporal gyri compared to those without ICDs. The connectivity of this area was increased mostly with the mesocorticolimbic system, positively with the orbitofrontal region, and negatively with both the right parahippocampus and the left caudate (IRCA). Moreover, the betweenness centrality of this area with the mesocorticolimbic system was lost in patients with ICDs (graph analysis). ICDs are associated in PD with the dysfunction of a network exceeding the mesocorticolimbic system, and especially the caudate, the parahippocampus, and the orbitofrontal cortex, remotely including the right middle and inferior temporal gyri. This latest area loses its central place with the mesocorticolimbic system through a connectivity dysregulation.
Impact of Medicare Advantage penetration and hospital competition on technical efficiency of nursing care in US intensive care units
Authors: Min Ari , Scott Linda D. , Park Chang , Vincent Catherine , Ryan Catherine J. , Lee Taewha
Published: April 2018

This study aimed to evaluate technical efficiency of US intensive care units and determine the effects of environmental factors on technical efficiency in providing quality of nursing care. Data were obtained from the 2014 National Database of Nursing Quality Indicators and the Centers for Medicare and Medicaid Services. Data envelopment analysis was used to estimate technical efficiency for each intensive care unit. Multilevel modeling was used to determine the effects of environmental factors on technical efficiency. Overall, Medicare Advantage penetration and hospital competition in a market did not create pressure for intensive care units to become more efficient by reducing their inputs. However, these 2 environmental factors showed positive influences on technical efficiency in intensive care units with certain levels of technical efficiency. The implications of the study results for management strategies and health policy may vary according to the levels of technical efficiency in intensive care units. Further studies are needed to examine why and how intensive care units with particular levels of technical efficiency are differently affected by certain environmental factors.
Identification of novel cyclin gene fusion transcripts in endometrioid ovarian carcinomas
Authors: Agostini Antonio , Brunetti Marta , Davidson Ben , Göran Tropé Claes , Heim Sverre , Panagopoulos Ioannis , Micci Francesca
Published: April 2018

Formation of fusion genes is pathogenetically crucial in many solid tumors. They are particularly characteristic of several mesenchymal tumors, but may also be found in epithelial neoplasms. Ovarian carcinomas, too, may harbor fusion genes but only few of these were found to be recurrent with a rate ranging from 0.5 to 5%. Because most attempts to find specific and recurrent fusion transcripts in ovarian carcinomas focused exclusively on high‐grade serous carcinomas, the situation in the other carcinoma subgroups remains largely uninvestigated as far as fusion genes are concerned. We performed transcriptome sequencing on a series of 34 samples from ovarian tumors that included borderline, clear cell, mucinous, endometrioid, low‐grade and high‐grade serous carcinomas in search of fusion genes typical of these subtypes. We found a total of 24 novel fusion transcripts. The PCMTDI‐CCNL2 fusion transcript, which involves a member of the cyclin family, was found recurrently involved but only in endometrioid carcinomas (4 of 18 tumors; 22%). We also found three additional fusion transcripts involving genes belonging to the cyclin family: ANXA5‐CCNA2 and PDE4D‐CCNB1 were detected in two endometrioid carcinomas, whereas CCNY‐NRG4 was identified in a clear cell carcinoma. The recurrent involvement of CCNL2 in four fusions and of three other genes of the cyclin family in three additional transcripts hints that deregulation of cyclin genes is important in the pathogenesis of ovarian carcinomas in general but of endometrioid carcinomas particularly.
Gold‐Catalyzed Polycyclization Toward Natural Products Synthesis
Authors: Toullec Patrick Y. , Michelet Véronique
Published: April 2018

Over the last years, gold catalysis has gained considerable significance in organic synthesis, since it allows atom economy and synthetic efficiency for the transformation of relatively simple substrates into valuable, highly complex molecular architectures. The gold‐catalyzed polycyclization reactions of alkynes and enynes have been particularly successful toward the synthesis of natural products. This review highlights the recent developments in polycyclization area according to the key gold‐catalyzed step.
The importance of body satisfaction to physical self‐concept and body mass index in Spanish adolescents
Authors: Sánchez‐Miguel Pedro Antonio , González Juan José Pulido , Sánchez‐Oliva David , Alonso Diana Amado , Leo Francisco Miguel
Published: April 2018

This research examines the association between measured body mass index (BMI) and the perception of BMI by young students. Moreover, this research tests the importance of BMI and self‐concept, in order to predict body dissatisfaction in high school students. The sample consisted of 2087 individuals from different high schools in Extremadura, Spain, both males (n = 1046) and females (n = 1041), ranging in age from 15 to 17 years old (M = 15.42; SD = 0.86). Initially, participants' BMIs were assessed through anthropometry. Later, all individuals were asked about their weight and height, and their self‐reported BMI was calculated. Participants also answered a questionnaire about their perception of self‐concept, as well as completed a test about body image perception using Stunkard images. Outcomes revealed that factors concerning self‐concept and perceived BMI explained body dissatisfaction. Finally, results are discussed with the aim of improving knowledge in body dissatisfaction context.
In vivo photoacoustic/ultrasonic dual‐modality endoscopy with a miniaturized full field‐of‐view catheter
Authors: Li Yan , Lin Riqiang , Liu Chengbo , Chen Jianhua , Liu Huadong , Zheng Rongqin , Gong Xiaojing , Song Liang
Published: April 2018

Endoscopy is an essential clinical tool for the diagnosis of gastrointestinal (GI) tract cancer. A photoacoustic system that elegantly combines optical and ultrasound endoscopy advantages by providing high‐sensitivity functional information and large imaging depth is a potentially powerful tool for GI tract imaging. Recently, several photoacoustic endoscopic imaging systems have been proposed and developed. However, the relatively large size and rigid length of the catheter make it difficult to translate them into wide clinical applications; while the existing system of a relatively small catheter, capable of in vivo animal imaging, is unable to acquire full (360°) field‐of‐view cross‐section images. In this study, we developed a photoacoustic/ultrasonic dual‐modality endoscopic system and a corresponding miniaturized, encapsulated imaging catheter, which provides a full 360° field‐of‐view. The diameter of the catheter is 2.5 mm, which is compatible with the 2.8‐mm instrumental channel of a conventional clinical optical endoscope. Using this system, we demonstrate in vivo 3‐dimensional endoscopic photoacoustic/ultrasonic imaging of the colorectum of a healthy Sprague Dawley rat, by depicting vasculature and morphology of the GI tract. The significantly improved imaging field of view, reduced catheter size, high‐quality imaging results suggest that the developed photoacoustic/ultrasonic dual‐modality endoscopy has a great potential to be translated into a broad range of clinical applications in gastroenterology.
Is the choice of a standard zeroth‐order hamiltonian in CASPT2 ansatz optimal in calculations of excitation energies in protonated and unprotonated schiff bases of retinal?
Authors: Wolański Łukasz , Grabarek Dawid , Andruniów Tadeusz
Published: April 2018

To account for systematic error of CASPT2 method empirical modification of the zeroth‐order Hamiltonian with Ionization Potential‐Electron Affinity (IPEA) shift was introduced. The optimized IPEA value (0.25 a.u.), called standard IPEA (S‐IPEA), was recommended but due to its unsatisfactory performance in multiple metallic and organic compounds it has been questioned lately as a general parameter working properly for all molecules under CASPT2 study. As we are interested in Schiff bases of retinal, an important question emerging from this conflict of choice, to use or not to use S‐IPEA, is whether the introduction of the modified zeroth‐order Hamiltonian into CASPT2 ansatz does really improve their energetics. To achieve this goal, we assessed an impact of the IPEA shift value, in a range of 0–0.35 a.u., on vertical excitation energies to low‐lying singlet states of two protonated (RPSBs) and two unprotonated (RSBs) Schiff bases of retinal for which experimental data in gas phase are available. In addition, an effect of geometry, basis set, and active space on computed VEEs is also reported. We find, that for these systems, the choice of S‐IPEA significantly overestimates both S0→S1 and S0→S2 energies and the best theoretical estimate, in reference to the experimental data, is provided with either unmodified zeroth‐order Hamiltonian or small value of the IPEA shift in a range of 0.05–0.15 a.u., depending on active space and basis set size, equilibrium geometry, and character of the excited state. © 2018 Wiley Periodicals, Inc.
Dipole moments of molecules with multi‐reference character from optimally tuned range‐separated density functional theory
Authors: Alipour Mojtaba
Published: April 2018

Dipole moment is the first nonzero moment of the charge density of neutral systems. If a density functional theory (DFT) method is able to yield accurate dipole moments, it should first provide an accurate geometry and then predict a reliable charge distribution for that geometry. In this respect, recent literatures have revealed that most DFT approximations work considerably better for single‐reference molecules with respect to multi‐reference ones, as may be expected from this fact that DFT utilizes a single configuration state function as reference function to represent the density. Putting together, it seems that as compared to the single‐reference systems, situation is slightly more involved in the case of dipole moment calculations of multi‐reference molecules. Effort to address this latter issue constitutes the cornerstone of the present investigation. To this end, we rely on a different approach where the new optimally (nonempirically) tuned range‐separated hybrid density functionals (OT‐RSHs) without invoking any empirical fitting are proposed for predicting the dipole moments of multi‐reference molecules containing both main‐group elements and transition metals. We have scanned the controlling factors of OT‐RSHs like short‐ and long‐range exchange contributions and range‐separation parameter with the aim of deriving the best performing models for the purpose. The obtained results unveil that, as compared to the standard range‐separated density functionals, our newly developed OT‐RSHs not only give an improved description on the dipole moments of the molecules with multi‐reference character but also the quality of their predictions is better than other conventional and recently proposed DFT approximations. © 2018 Wiley Periodicals, Inc.
Exact and exclusive electron localization indices within QTAIM atomic basins
Authors: de Lange Jurgens H. , Cukrowski Ignacy
Published: April 2018

Novel measures of electron (de)localization within the Quantum Theory of Atoms in Molecules (QTAIM) atomic basins are presented which, unlike orthodox localization indices (LIs), are fully exclusive and can be easily visualized. This work shows that QTAIM‐defined LIs describe a portion of interatomic delocalized electrons; hence, the chemical/physical interpretation of orthodox LIs is misleading. Using the recently introduced Fragment, Atomic, Localized, Delocalized, and Interatomic (FALDI) density decomposition technique we derive two novel sets of LIs and delocalization indices (DIs), by accounting for the overlap between localized and delocalized density functions. The FALDI‐based LIs and DIs perfectly recover chemically expected core and bonded electron count. Usefulness of new (de)localization indices and their 3D representations were demonstrated on a number of examples, including formamide and benzene. We therefore expect that the scheme reported in this work will provide a valuable stepping stone between classical conceptual chemistry and quantum chemical topology. © 2018 Wiley Periodicals, Inc.
Copolymerization of carbon dioxide and propylene oxide by several metallosalen‐based bifunctional catalysts
Authors: Zhu Wenkai , Du Longchao , Qian Siyu , Yang Qingsong , Song Wanjie
Published: April 2018

A series of new metallosalen‐based bifunctional catalysts with Co(III), Cr(III), Fe(III), Mn(III), and Ni(III) were synthesized for the first time, and a detailed study on the mechanism of the copolymerization of CO2 and propylene oxide (PO) was performed. Meanwhile, the impact factors of the reaction conditions (metal cations, temperature, CO2 pressure, and reaction time) on catalytic activity and selectivity were investigated. The results indicated that, with the increase of temperature, both the catalyst efficiency and the molecular weight of the copolymer decrease for all the five complexes. The salen‐Co(III) complex demonstrated higher activity under mild conditions: reaction temperature at 30 °C, copolymerization time of 24 hr, and 2 MPa of CO2 pressure. The DSC curve indicated that the PPC by the salen‐Co(III) complex has the highest Tg of 46.19 °C. DTGA curves demonstrated that there were two thermal degradation peaks: the first is for the ester bond, and the second is for the CC bond.
When Seeking the Best Brings Out the Worst in Consumers: Understanding the Relationship between a Maximizing Mindset and Immoral Behavior
Authors: Goldsmith Kelly , Roux Caroline , Ma Jingjing
Published: April 2018

Consumers often adopt a goal to choose “the best” option: be it the best value for their money, the product with the highest quality, or the product that offers the best match to their idiosyncratic preferences. Prior work has characterized this orientation as a “maximizing mindset,” and has demonstrated that the adoption of a maximizing mindset can lead to both positive and negative consequences for the self. However, to date, little is known about if a maximizing mindset might have consequences beyond the self (i.e., for others and/or society). The current article addresses this gap by demonstrating that consumers who adopt a maximizing mindset (vs. a neutral mindset) are subsequently more likely to engage in immoral behaviors. Further, we demonstrate that this effect occurs because a maximizing mindset activates cognitions related to scarcity. In doing so, the current research offers a more nuanced understanding of the psychological and behavioral consequences of a maximizing mindset and identifies a maximizing mindset as an antecedent to cognitions related to scarcity and immoral behaviors.
Diversification of 6‐bromo‐2‐substituted Pyridine Derivatives via Suzuki‐Miyaura Cross‐Coupling
Authors: Lambert Abigail E. , Carrick Jesse D.
Published: April 2018

The functionalized pyridine ring is a ubiquitous moiety in numerous research areas including materials, natural products, as well as agrochemicals and is a strategic synthon for heteroaromatic synthetic method development. Pyridinyl ligand scaffolds are also frequently incorporated into the study of metal complexes for pharmaceutical applications or separation science. Convergent access to advanced synthons is critical to experimentally defining structure activity relationships and improvement of molecular performance in the aforementioned areas. The current work describes an efficient catalyst/ligand combination for accessing 2‐acetyl‐ and 2‐procarbonyl substituted pyridines via Suzuki‐Miyaura cross‐coupling with various organotrifluoroborates. Twenty examples are described with carbonyl and procarbonyl functional groups which afford subsequent access to diversified unsymmetric ketones. Substrate scope and limitation in addition to a scale up experiment are reported.
Linkage and retention in HCV care for HIV‐infected populations: early data from the DAA era
Authors: Sacks‐Davis Rachel , Doyle Joseph S , Rauch Andri , Beguelin Charles , Pedrana Alisa E , Matthews Gail V , Prins Maria , van der Valk Marc , Klein Marina B , Saeed Sahar , Lacombe Karine , Chkhartishvili Nikoloz , Altice Frederick L , Hellard Margaret E
Published: April 2018

Introduction

There is currently no published data on the effectiveness of DAA treatment for elimination of HCV infection in HIV‐infected populations at a population level. However, a number of relevant studies and initiatives are emerging. This research aims to report cascade of care data for emerging HCV elimination initiatives and studies that are currently being evaluated in HIV/HCV co‐infected populations in the context of implementation science theory.

Methods

HCV elimination initiatives and studies in HIV co‐infected populations that are currently underway were identified. Context, intervention characteristics and cascade of care data were synthesized in the context of implementation science frameworks.

Results

Seven HCV elimination initiatives and studies were identified in HIV co‐infected populations, mainly operating in high‐income countries. Four were focused mainly on HCV elimination in HIV‐infected gay and bisexual men (GBM), and three included a combination of people who inject drugs (PWID), GBM and other HIV‐infected populations. None were evaluating treatment delivery in incarcerated populations. Overall, HCV RNA was detected in 4894 HIV‐infected participants (range within studies: 297 to 994): 48% of these initiated HCV treatment (range: 21% to 85%; within studies from a period where DAAs were broadly available the total is 57%, range: 36% to 74%). Among studies with treatment completion data, 96% of 1109 initiating treatment completed treatment (range: 94% to 99%). Among those who could be assessed for sustained virological response at 12 weeks (SVR12), 1631 of 1757 attained SVR12 (93%, range: 86% to 98%).

Conclusions

Early results from emerging research on HCV elimination in HIV‐infected populations suggest that HCV treatment uptake is higher than reported levels prior to DAA treatment availability, but approximately half of patients remain untreated. These results are among diagnosed populations and additional effort is required to increase diagnosis rates. Among those who have initiated treatment, completion and SVR rates are promising. More data are required in order to evaluate the effectiveness of these elimination programmes in the long term, assess which intervention components are effective, and whether they need to be tailored to particular population groups.
Approaches for simplified HCV diagnostic algorithms
Authors: Fourati Slim , Feld Jordan J , Chevaliez Stéphane , Luhmann Niklas
Published: April 2018

Introduction

In the light of the advances in HCV antiviral therapy, global control of HCV infection becomes feasible but depends on the capacity of countries to identify infected people and to offer them treatment. To achieve the WHO goal which targets a diagnosis rate of 90% by 2030, simplification of screening and diagnosis will be crucial.

Methods

Published literature, unpublished data and expert consensus were used to determine key parameters, including point‐of‐care, rapid diagnostic testing, screening, the use of HCV core Ag and dried blood spots; starting from 2008 until November 2017. In addition, a manual search was undertaken to detect relevant papers or websites related to specific data from countries which underwent or are planning a programme of HCV elimination.

Results

Several strategies have been developed and evaluated these last years to simplify and facilitate access to screening and diagnosis, the development of reliable HCV core antigen tests and new nucleic acid amplification technologies for use in decentralized settings. In high prevalence settings, a one‐step screening and diagnosis strategy could simplify diagnostic algorithms provided the cost is reduced. Finally, genotyping may no longer be required in the context of availability of pangenotypic antiviral therapy.

Conclusions

Despite relevant advances in HCV screening and diagnosis, the overall diagnosis package is still too expensive today and efforts must be made to allow generalized implementation of reliable tests in low and middle income countries. These efforts will be key factors to foster a real public health approach to HCV elimination.
Inhibiting focal adhesion kinase (FAK) blocks IL-4 induced VCAM-1 expression and eosinophil recruitment in vitro and in vivo
Authors: Aulakh Gurpreet K , Petri Björn , Wojcik Katarzyna M , Colarusso Pina , Lee James J , Patel Kamala D
Published: April 2018

Leukocyte recruitment plays a critical role during both normal inflammation and chronic inflammatory diseases, and ongoing studies endeavor to better understand the complexities of this process. Focal adhesion kinase (FAK) is well known for its role in cancer, yet it also has been shown to regulate aspects of neutrophil and B16 melanoma cell recruitment by rapidly influencing endothelial cell focal adhesion dynamics and junctional opening. Recently, we found that FAK related non-kinase (FRNK), a protein that is often used as a FAK dominant negative, blocked eosinophil transmigration by preventing the transcription of vascular cell adhesion molecule-1 (VCAM-1) and eotaxin-3 (CCL26). Surprisingly, the blocking occurred even in the absence of endogenous FAK. To better understand the role of FAK in leukocyte recruitment, we used a FAK-specific inhibitor (PF-573228) and determined the effect on IL-4 induced eosinophil recruitment in vitro and in vivo. PF-573228 prevented the expression of VCAM-1 and CCL26 expression in IL-4-stimulated human endothelial cells in vitro. As a result, eosinophil adhesion and transmigration were blocked. PF-572338 also prevented IL-4-induced VCAM-1 expression in vivo. Using brightfield intravital microscopy, we found that PF-573228 decreased leukocyte rolling flux, adhesion, and emigration. We specifically examined eosinophil recruitment in vivo by using an eosinophil-GFP reporter mouse and found PF-573228 attenuated eosinophil emigration. This study reveals that a FAK inhibitor influences inflammation through its action on eosinophil recruitment.

FAK inhibitor affects eosinophil recruitment in vivo using a new eosinophil reporter animal.
Altered fecal microbiota composition in all male aggressor‐exposed rodent model simulating features of post‐traumatic stress disorder
Authors: Gautam Aarti , Kumar Raina , Chakraborty Nabarun , Muhie Seid , Hoke Allison , Hammamieh Rasha , Jett Marti
Published: April 2018

The bidirectional role of gut–brain axis that integrates the gut and central nervous system activities has recently been investigated. We studied “cage‐within‐cage resident‐intruder” all‐male model, where subject male mice (C57BL/6J) are exposed to aggressor mice (SJL albino), and gut microbiota‐derived metabolites were identified in plasma after 10 days of exposure. We assessed 16S ribosomal RNA gene from fecal samples collected daily from these mice during the 10‐day study. Alpha diversity using Chao indices indicated no change in diversity in aggressor‐exposed samples. The abundance profile showed the top phyla were Firmicutes and Bacteroidetes, Tenericutes, Verrucomicrobia, Actinobacteria and Proteobacteria, respectively. The phyla Firmicutes and Bacteroidetes are vulnerable to PTSD‐eliciting stress and the Firmicutes/Bacteroidetes ratio increases with stress. Principal coordinate analysis showed the control and aggressor‐exposed samples cluster separately where samples from early time points (day 1‐3) clustered together and were distinct from late time points (day 4‐9). The genus‐based analysis revealed all control time points clustered together and aggressor‐exposed samples had multiple clusters. The decrease in proportion of Firmicutes after aggressor exposure persisted throughout the study. The proportion of Verrucomicrobia immediately decreased and was significantly shifted at most of the later time points. The genus Oscillospira, Lactobacillus, Akkermansia and Anaeroplasma are the top four genera that differed between control and stressor‐exposed mice. The data showed immediate effect on microbiome composition during a 10 day time period of stress exposure. Studying the longitudinal effects of a stressor is an important step toward an improved mechanistic understanding of the microbiome dynamics.
College Students' Experiences of Childhood Developmental Traumatic Stress: Resilience, First‐Year Academic Performance, and Substance Use
Authors: Arnekrans Allison K. , Calmes Stephanie A. , Laux John M. , Roseman Christopher P. , Piazza Nick J. , Reynolds Jennifer L. , Harmening Debra , Scott Holly L.
Published: April 2018

Developmental trauma—distressing childhood experiences that include mistreatment, interpersonal violence, abuse, assault, and neglect—is associated with substance use and poor academic performance. The authors investigated the links between developmental trauma, grade point average, substance use, and resilience among first‐year college students (N = 169). The results indicate there is a significant relationship between cumulative trauma and self‐reported substance use.
Post‐translational cleavage pattern of Lupinus angustifolius γ‐conglutin
Authors: Czubiński Jarosław , Montowska Magdalena , Fornal Emilia
Published: April 2018

BACKGROUND

Protein post‐translational modifications are a key element for the functional diversity of the proteome. The modifications generally refer to the addition of functional groups to certain proteins; however, proteolytic cleavage is also one of the relevant events during protein maturation. γ‐Conglutin is a unique protein fraction present in lupin seeds that is marked by numerous unusual properties. This protein fraction undergoes very complex post‐translational maturation. Unfortunately, the precise mechanism of γ‐conglutin post‐translational processing is not yet fully understood.

RESULTS

Two independent methods were used to study γ‐conglutin post‐translational cleavage processing. Edman N‐terminal sequencing indicates that the signal peptide is processed at Tyr34, while α‐ and β‐subunit cleavage takes place between Ser295 and Ser296. High‐resolution mass spectrometry revealed a great diversity of N‐terminal sequences of γ‐conglutin α‐subunit. However, most abundant peptides also began from Tyr34. Mass spectrometric analyses additionally confirmed the subunit cleavage position between two serine residues.

CONCLUSIONS

The results indicate that the proteolytic processing of γ‐conglutin signal peptide is not precise. On the other hand, the post‐translational cleavage between α‐ and β‐subunits of γ‐conglutin is very conserved. Interestingly, the results also indicate that proteolytic processing leading to the formation of two subunits of γ‐conglutin is incomplete, leaving a certain amount of the protein in an uncut form. © 2018 Society of Chemical Industry