bluuebunny/crossref_metadata_2025_split huggingface dataset:
Dysfunctional BTN3A together with deregulated immune checkpoints and type I/II IFN dictate defective interplay between pDCs and γδ T cells in melanoma patients, which impacts clinical outcomes
Authors: Girard Pauline , Sosa Cuevas Eleonora , Ponsard Benedicte , Mouret Stephane , Gil Hugo , Col Edwige , De Fraipont Florence , Sturm Nathalie , Charles Julie , Manches Olivier , Chaperot Laurence , Aspord Caroline 
Published: November 2021

AbstractObjectivespDCs and γδ T cells emerge as potent immune players participating in the pathophysiology of cancers, yet still remaining enigmatic while harbouring a promising potential for clinical translations. Despite strategic and closed missions, crosstalk between pDCs and γδ T cells has not been deciphered yet in cancers, especially in melanoma where the long‐term control of the tumor still remains a challenge.MethodsThis prompted us to explore the interplay between pDCs and γδ T cells in the context of melanoma, investigating the reciprocal features of pDCs or γδ T cells, the underlying molecular mechanisms and its impact on clinical outcomes.ResultsTLRL‐activated pDCs from the blood and tumor infiltrate of melanoma patients displayed an impaired ability to activate, to modulate immune checkpoints and trigger the functionality of γδ T cells. Conversely, γδ T cells from the blood or tumor infiltrate of melanoma patients activated by PAg were defective in triggering pDCs’ activation and modulation of immune checkpoints, and failed to elicit the functionality of pDCs. Reversion of the dysfunctional cross‐talks could be achieved by specific cytokine administration and immune checkpoint targeting. Strikingly, we revealed an increased expression of BTN3A on circulating and tumor‐infiltrating pDCs and γδ T cells from melanoma patients, but stressed out the potential impairment of this molecule.ConclusionOur study uncovered that melanoma hijacked the bidirectional interplay between pDCs and γδ T cells to escape from immune control, and revealed BTN3A dysfunction. Such understanding will help harness and synergise the power of these potent immune cells to design new therapeutic approaches exploiting their antitumor potential while counteracting their skewing by tumors to improve patient outcomes.
Nonideal nest box selection by tree swallows breeding in farmlands: Evidence for an ecological trap?
Authors: Courtois Ève , Garant Dany , Pelletier Fanie , Bélisle Marc 
Published: November 2021

AbstractAnimals are expected to select a breeding habitat using cues that should reflect, directly or not, the fitness outcome of the different habitat options. However, human‐induced environmental changes can alter the relationships between habitat characteristics and their fitness consequences, leading to maladaptive habitat choices. The most severe case of such nonideal habitat selection is the ecological trap, which occurs when individuals prefer to settle in poor‐quality habitats while better ones are available. Here, we studied the adaptiveness of nest box selection in a tree swallow (Tachycineta bicolor) population breeding over a 10‐year period in a network of 400 nest boxes distributed along a gradient of agricultural intensification in southern Québec, Canada. We first examined the effects of multiple environmental and social habitat characteristics on nest box preference to identify potential settlement cues. We then assessed the links between those cues and habitat quality as defined by the reproductive performance of individuals that settled early or late in nest boxes. We found that tree swallows preferred nesting in open habitats with high cover of perennial forage crops, high spring insect biomass, and high density of house sparrows (Passer domesticus), their main competitors for nest sites. They also preferred nesting where the density of breeders and their mean number of fledglings during the previous year were high. However, we detected mismatches between preference and habitat quality for several environmental variables. The density of competitors and conspecific social information showed severe mismatches, as their relationships to preference and breeding success went in opposite direction under certain circumstances. Spring food availability and agricultural landscape context, while related to preferences, were not related to breeding success. Overall, our study emphasizes the complexity of habitat selection behavior and provides evidence that multiple mechanisms may potentially lead to an ecological trap in farmlands.
The impact of a community‐based heart failure multidisciplinary team clinic on healthcare utilization and costs
Authors: Weinstein Jean Marc , Greenberg Dan , Sharf Amir , Simon‐Tuval Tzahit 
Published: November 2021

AbstractAimsMultidisciplinary team (MDT) management in heart failure (HF) is recommended to reduce mortality and HF hospitalization. We investigated whether an MDT in a community‐based HF unit (HFU) impacted patients' healthcare utilization (HCU) and costs.Methods and resultsA retrospective cohort study was conducted among HF patients who visited at least once in a regional community‐based HFU, established for ambulatory specialist care for New York Heart Association Functional Classes III and IV, between January 2012 and August 2019. HCU data were obtained from the health maintenance organization's claims data for 12 months before and after first HFU visit. Multivariable generalized estimating equation models were specified for the annual average change in total healthcare utilization and hospitalization costs. Our cohort consisted of 962 patients, of whom 843 (87.6%) completed at least 12 months of follow‐up (Group A) and 119 (12.4%) died within 12 months following their first visit (Group B). Both groups were comparable regarding sex, socio‐economic status, Charlson Comorbidity Index, ischaemic heart disease, and/or carotid artery disease. Those who died within 12 months were older and had more hypertension, diabetes, chronic renal disease, and malignancy. There was a significant reduction in the total average annual HCU costs of the entire study population 12 months after the first HFU visit [$12 675 (±17 210) after vs. $13 188 (±15 011) before, P = 0.014]. This was driven by a reduction in costs among patients who completed 12 months of follow‐up [$11 955 (±17 352) after vs. $13 112 (±15 268) before, P < 0.001], whereas an increase in these costs was observed among patients who died during follow‐up [$17 774 (±15 292) after vs. $13 728 (±13 093) before, P = 0.015]. These opposite trends stem mainly from a decrease [$3540 (±8991) after vs. $4941 (±6806) before, P < 0.001] vs. increase [$10 932 (±11 660) after vs. $6733 (±7215) before, P = 0.002] in hospitalization costs of these groups, respectively. The multivariable models revealed that patients who died within 12 months following the first visit to the HFU demonstrated a significant increase of 57% in hospitalization costs following their first visit [relative risk (RR) = 1.57, 95% confidence interval (CI): 1.20–2.05, P = 0.001], whereas there was a decrease of 34% in the hospitalization costs of patients who completed 12 months of follow‐up after their first visit (RR = 0.66, 95% CI: 0.54–0.81, P < 0.001). The entire cohort demonstrated 27% decrease in hospitalization costs following their first HFU visit (RR = 0.73, 95% CI: 0.62–0.87, P < 0.001).ConclusionsIntensification of therapy by a dedicated MDT significantly reduced healthcare utilization and costs, predominantly due to a decrease in hospitalizations.
Stereoisomerism in Tetrametallic Propeller‐Like Complexes: A Solid‐State and Solution NMR Study on a Tetragallium(III) Derivative
Authors: Cornia Andrea , Mucci Adele , Briganti Matteo , Bridonneau Nathalie , Nava Andrea , Nicolini Alessio 
Published: November 2021

AbstractTetragallium(III) complex in [Ga4(L4‐Py)2(dpm)6] ⋅ EtOH, with H3L4‐Py=2‐(hydroxymethyl)‐2‐(pyridin‐4‐yl)propane‐1,3‐diol and Hdpm=dipivaloylmethane, was investigated as a diamagnetic analogue of tetrametallic, propeller‐like single‐molecule magnets (SMMs). The chiral molecular structure partitions the six CH2 protons of each tripodal (L4‐Py)3− ligand into two diastereotopic sets. The two signals were clearly detected by 1H NMR spectroscopy in C6D6, proving that Λ and Δ enantiomers interconvert slowly over NMR timescale. Density functional theory calculations provided quantitative agreement with the observed values of chemical shifts and scalar coupling constants across both geminal and long‐range interaction pathways. The solid‐state structure suggests the occurrence of a lower symmetry stereoisomer (27 mol%), which was clearly identified in the NMR spectra. Since high spin Fe3+ forms distinctly more inert complexes than Ga3+, comparable or greater configurational stability is expected for the isostructural FeIII4, FeIII3CrIII, and FeIII3VIII SMMs, which are difficult to investigate by solution NMR because of the strong paramagnetism.
Mixed‐Ligand Oxidovanadium(IV/V) Complexes Chelated by α‐Hydroxycarboxylate and 2‐(1H‐Imidazol‐2‐yl)pyridine: Localized Structures and Gas Adsorption
Authors: Xie Zhen‐Lang , Yuan Chang , Jin Wan‐Tin , Zhou Zhao‐Hui 
Published: November 2021

AbstractMonomeric oxidovanadium(IV) citrate and malate, [VO(H2cit)(Him‐py)] ⋅ H2O (1) and [VO(R,S‐Hmal)(Him‐py)] (2), and an additive of mixed‐valence oxidovanadium(IV/V) (1H‐imidazol‐2‐yl)pyridine [V2O2(μ2‐O)(glyc)(Him‐py)2(im‐py)] ⋅ [VO2(Him‐py)(im‐py)] ⋅ 9.5H2O (3) [Him‐py=2‐(1H‐imidazol‐2‐yl)pyridine, H4cit=citric acid, R,S‐H3mal=R,S‐malic acid, H2glyc=glycolic acid] have been isolated from the reactions of vanadyl sulfate with α‐hydroxycarboxylate (citrate, malate, and glycolate) and 2‐(1H‐imidazol‐2‐yl)pyridine in acidic solutions, respectively. The citrate or malate chelates to vanadium atom tridentately through α‐hydroxy, α‐carboxy and β‐carboxy groups that different with bidentate glycolate, while the other β‐carboxy acidic group of citrate in 1 remains uncoordinated and participates in strong hydrogen bonds with water molecules. Further substitution of 2‐(1H‐imidazol‐2‐yl)pyridine for citrate in 1 results in the formation of [VO2(Him‐py)(im‐py)]3 ⋅ 4.5H2O (4) in basic solution. With comparable chelation, 1 shares a similar V−Oα‐hydroxy distance [2.214(2) Å] with that observed in FeV‐cofactor [2.156av Å],[1] where a protonated model is suggested for the local chelated environment of FeV‐cofactor in citrate‐substituted V‐nitrogenase variant. Interestingly, 2D porous structure of additive 3 features two types of irregular microchannels with diameters of 16.6 and 6.4 Å, respectively, which can adsorb CO2 and O2 for 9.28 and 29.68 mg/g at 29.89 bar, respectively, while little or no adsorption for H2, N2, and CH4.
Noncovalent Intra‐ and Intermolecular Interactions in Peri‐Substituted Pnicta Naphthalene and Acenaphthalene Complexes
Authors: Gehlhaar Alexander , Wölper Christoph , van der Vight Felix , Jansen Georg , Schulz Stephan 
Published: November 2021

AbstractFive peri‐substituted naphthalene and acenaphthalene complexes (Ph2Pn)2Naph (E=Sb 1, Bi 3), (Ph2Sb)2Acenaph (2), (Ph2Bi)(Me3Sn)Naph (4) and (PhBiNaph)2 (5) were synthesized and characterized in solution (1H, 13C NMR, IR) and in the solid‐state (sc‐XRD). 1–5 show different types of noncovalent intermolecular interactions in the solid‐state including Naph−H⋅⋅⋅π, π⋅⋅⋅π and Bi⋅⋅⋅π (5) contacts, which were exemplarily (5) quantified by use of density functional theory and local coupled cluster electronic structure theory calculations, demonstrating that the Bi⋅⋅⋅π contact provides the main stabilizing contribution. Symmetry‐adapted intermolecular perturbation theory calculations showed that this and other contacts are dominated by London dispersion interactions.
Synthesis of Azido‐Dienediols by Enzymatic Dioxygenation of Benzylazides: An Experimental and Theoretical Study
Authors: de la Sovera Victoria , Martínez Sebastián , Umpiérrez Diego , Vila María Agustina , Gonzalez David , Seoane Gustavo , Veiga Nicolás , Carrera Ignacio 
Published: November 2021

AbstractAllylic azides are versatile structural motifs in organic synthesis because the proximal double bond enables a [3,3]‐sigmatropic rearrangement, named as the Winstein rearrangement. In this work, an experimental and theoretical study on the double Winstein rearrangement occurring in azidodienediols derived from the biocatalytic dihydroxylation of substituted benzylazides is presented. Substrates bearing a methyl group at the ortho or meta position produced exclusively rearranged exo‐diendiols with the azide group anti to the diol moiety as the major constituent. In the case of para methyl substrates, an equilibrium mixture of rearranged and non‐rearranged products was observed, indicating that a full conversion to the exo‐dienediols is not possible within this substitution pattern. On the other hand, the presence of a chloro substituent in the diene moiety completely precluded the Winstein rearrangement to take place, giving rise exclusively to the traditional cis‐cyclohexadienediols. The observed results were analyzed to determine the mechanistic and kinetic aspects and scope limitations of the reaction as a synthetic tool.
Relative contributions of the nervous system, spinal tissue and psychosocial health to non‐specific low back pain: Multivariate meta‐analysis
Authors: Tagliaferri Scott D. , Ng Sin‐Ki , Fitzgibbon Bernadette M. , Owen Patrick J. , Miller Clint T. , Bowe Steven J. , Belavy Daniel L. 
Published: November 2021

AbstractBackground and ObjectivesNervous system, psychosocial and spinal tissue biomarkers are associated with non‐specific low back pain (nsLBP), though relative contributions are unclear.Databases and Data TreatmentMEDLINE, EMBASE, CINAHL, PsycINFO and SPORTDiscus were searched up to 25 March 2020. Related reviews and reference lists were also screened. Observational studies examining structural and functional nervous system biomarkers (e.g. quantitative sensory tests, structural and functional brain measures), psychosocial factors (e.g. mental health, catastrophizing) and structural spinal imaging biomarkers (e.g. intervertebral disc degeneration, paraspinal muscle size) between nsLBP and pain‐free controls were included. For multivariate meta‐analysis, two of three domains were required in each study. Random‐effects pairwise and multivariate meta‐analyses were performed. GRADE approach assessed evidence certainty. Newcastle‐Ottawa scale assessed risk of bias. Main outcomes were the effect size difference of domains between nsLBP and pain‐free controls.ResultsOf 4519 unique records identified, 33 studies (LBP = 1552, referents = 1322) were meta‐analysed. Psychosocial state (Hedges’ g [95%CI]: 0.90 [0.69–1.10], p < 0.001) in nsLBP showed larger effect sizes than nervous system (0.31 [0.13–0.49], p < 0.001; difference: 0.61 [0.36–0.86], p < 0.001) and spine imaging biomarkers (0.55 [0.37–0.73], p < 0.001; difference: 0.36 [0.04–0.67], p = 0.027). The relationship between domains changes depending on if pain duration is acute or chronic.ConclusionsPsychosocial effect sizes in nsLBP are greater than those for spinal imaging and nervous system biomarkers. Limitations include cross‐sectional design of studies included and inference of causality. Future research should investigate the clinical relevance of these effect size differences in relation to pain intensity and disability.Study RegistrationPROSPERO‐CRD42020159188.SignificanceSpinal structural lesions (e.g. intervertebral disc degeneration), psychosocial (e.g. depression) and nervous system factors (detected by e.g. quantitative sensory tests, structural and functional measures) contribute to non‐specific low back pain. However, psychosocial factors may be more compromised than nervous system and spinal imaging biomarkers. This relationship depends on if the pain is acute or chronic. These findings underscore that the ‘non‐specific’ label in back pain should be reconsidered, and more specific multidimensional categories evaluated to guide patient management.
Zn‐doped NiCo2O4 as Modified Electrode Nanomaterials for Enhanced Electrochemical Detection Performance of Cu(II)
Authors: Jiang Rong , Chen Long , Bai Xuemei , Ye Jiahui , Luo Yun , Wang Liping , Fan Changchun , Li Haoquan , Shi Yulin , Xu Yisheng 
Published: November 2021

AbstractA novel nano‐ternary spinel oxides of Zn−Ni‐Co−O are synthesized via the coprecipitation method and used for detection towards Cu(II). The Zn doping effect on morphologies and microstructures of ZnxNi1‐xCo2O4 (x=0, 0.2, 0.4, 0.6, 0.8, 1.0) is systematically characterized and investigated. At the x of 0.4, the prepared Zn0.4Ni0.6Co2O4 modified electrode nanomaterials can realize electrochemical ultratrace detection of Cu(II), which shows the lowest detection limit of 1.96 nM with a linear range of 0.1 μM∼1.0 μM and the highest sensitivity of 15.2 μA/μM. Meanwhile, Zn0.4Ni0.6Co2O4 modified electrodes exhibit excellent repeatability (relative standard deviation (RSD) of 0.34 %), reproducibility (RSD of 0.3 %), stability (RSD of 3.0 %) as well as anti‐interference analysis, which has been successfully applied in the actual water environment. These results indicate that ZnxNi1‐xCo2O4 nanoparticles as a promising modified electrode materials for the electrochemical detection Cu(II).
Effect of skimming layer in an electroosmotically driven viscoelastic fluid flow over charge modulated walls
Authors: Mahapatra Bimalendu , Bandopadhyay Aditya 
Published: November 2021

AbstractWe report a numerical study on the effect of the skimming layer in an EOF of Oldroyd‐B fluid over charge modulated walls. Three types of flow conditions were identified on the basis of the relative thickness of the skimming layer and the electrical double layer. We observe maximum slip velocity magnitude when the skimming layer thickness is very less than the thickness of the electrical double layer. For higher skimming layer thickness compared to the thickness of electrical double layer, slip velocity magnitude attenuates, and the polymeric stress inside the skimming layer becomes zero. Enhanced fluid elasticity generates asymmetric flow structures inside the microchannel, which can also be achieved by imposing an asymmetric surface charge along the channel walls. Our present analysis highlights the complex flow dynamics of the EOF of biofluids/polymeric fluids with a near‐wall region depleted of macro‐molecules.
In Vivo Transformation of a Novel Polyfluoroether Surfactant
Authors: Folkerson Andrew P. , Joudan Shira , Mabury Scott A. , D'eon Jessica C. 
Published: November 2021

Abstract
Per- and polyfluoroalkyl substances are a class of fluorochemicals that can degrade into perfluoroalkyl acids, which are well known to be persistent in the environment. It is thus important that novel fluorinated surfactants be designed to degrade into small, nonbioaccumulative products. We report the biotransformation and elimination kinetics of one such novel polyfluorinated surfactant, di(polyfluoroether thioether(S)-oate) sulfonate (diFESOS), and its metabolites. Biotransformation was investigated in vitro using S9 liver fractions and in vivo in Sprague–Dawley rats. Rats dosed by oral gavage with diFESOS were found to have relatively fast elimination kinetics, with half-lives on the order of hours, compared with legacy fluorinated surfactants such as the disubstituted polyfluoroalkyl phosphates that have half-lives on the order of days. To interrogate degradation of the polyfluorinated chain, rats were then dosed with a polyfluoroether thioether alcohol (a suspected product of carboxylate cleavage of diFESOS) either orally or intravenously, and the novel metabolite 2H-3:2 polyfluoroether sulfonic acid (2H-3:2 PFESA) was identified. Perfluoropropionic acid was detected in rat urine and is likely a terminal product. The blood of orally dosed rats contained higher levels of metabolites than the blood of intravenously dosed rats, suggesting the importance of metabolism in the gut and liver. Elimination kinetics of all the novel metabolites were faster than their fully fluorinated counterparts. Environ Toxicol Chem 2021;40:3328–3336. © 2021 SETAC
Abstract
In vivo biotransformation and kinetics of a novel highly functionalized fluorinated surfactant. FESCA = polyfluoroether carboxylic acid; 2H-3:2 PFESA = 2H-3:2 polyfluoroether sulfonic acid.
Effect of boiling and oven roasting on some physicochemical properties of sunflower seeds produced in Far North, Cameroon
Authors: Tenyang Noel , Ponka Roger , Tiencheu Bernard , Tonfack Djikeng Fabrice , Womeni Hilaire Macaire 
Published: November 2021

AbstractThe effects of different processing methods on proximate composition, total phenolic content, antioxidant activity, lipid oxidation, and mineral contents of sunflower seeds produced in Far North Region of Cameroon were evaluated. Mean moisture, ash, lipid, protein, fiber, and carbohydrate contents of raw sunflower seeds were 6.60%, 2.55%, 44.65%, 20.17%, 4.08%, and 21.25%, respectively. The changes in moisture, ash (excepted in boiled samples), lipid, protein, fiber, and carbohydrate (excepted in roasted samples) were found to be significant for all cooking methods. Ash and lipid contents of samples roasted at 120°C were found to be significant when compared with other cooking methods. Antioxidant activity increased with treatment. After processing, the acid, peroxide, and thiobarbituric acid values increased significantly, whereas iodine value decreased. The roasting process improved the induction time, and samples roasted at 120°C were found to have the highest induction time (2.29 ± 0.09 hr). Raw sunflower seeds were good sources of potassium (K), magnesium (Mg), calcium (Ca), iron (Fe), zinc (Zn), and manganese (Mn). Increase in contents of Ca, Mg, Zn, Cu, and Fe was observed during processing. Roasting compared with boiling appeared to be the best cooking method of sunflower seeds concerning nutrient content, antioxidant stability, and lipid stability.
Assessment of thermodynamic performance of a 20 kW high‐temperature electrolysis system using advanced exergy analysis
Authors: Li Guoliang , Xiao Guoping , Guan Chengzhi , Hong Chunfeng , Yuan Benfeng , Li Tao , Wang Jian‐Qiang 
Published: November 2021

AbstractThe thermal efficiency of the high‐temperature solid oxide electrolysis cell system for steam electrolysis has drawn extensive concern in the energy conversion field. This work presents a thermodynamic investigation of a high‐temperature steam electrolysis system by conventional and advanced exergy analyses. A steady‐state simulation of a 20 kW high‐temperature steam electrolysis system is performed for system performance analysis. The thermal inefficiency of each component in the system is revealed by conventional exergy analysis. The predictions show the system exergy efficiency is 49.98%, H2‐compressor has the largest exergy destruction (6773.6 W, 39.16% of the total exergy destruction). Through advanced exergy analysis, the impacts of the interactions among components and the technical limitation with each component are considered. The results indicate the H2‐compressor has the highest exergy saving potential owing to the largest avoidable exergy destruction (1935 W), followed by the stack and vapor generator. Thus, the solid oxide electrolysis cell stack, H2‐compressor, and vapor generator have tremendous potential in energy conservation. Advanced exergy analysis also indicates the interactions among components have less influence on the exergy destruction which means most measures toward improving high‐temperature steam electrolysis systems should be taken to improving each component itself rather than interconnections among components.