Contribution of emissions from the oil sands activities in Alberta, Canada to atmospheric concentration and deposition of nitrogen and sulfur species at a downwind site.

Oil sands activities in the Athabasca Oil Sands Region in Alberta, Canada, are large sources of atmospheric NOx and SO2. This study investigated the impact of oil sands emissions on the atmospheric deposition of nitrogen and sulfur species at a downwind site, about 350 km from the oil sands facilities. Measurement data are from the Canadian Air and Precipitation Monitoring Network (CAPMoN) from 2015 to 2019, including ambient concentrations of HNO3, pNO3-, NO2, pNH4+, NH3, SO2, pSO42- and base cations, as well as concentrations of NO3-, SO42-, NH4+, and base cations in precipitation. Sector analysis of air mass back trajectories was conducted to distinguish measurements with different air mass origins. Median atmospheric concentrations and dry deposition fluxes of HNO3, pNO3-, NO2, pNH4+, pSO42-, and SO2 on days when the air masses came from the oil sands sector were significantly greater than those with the "Clean" sector by 34-67%, whereas the difference in NH3 concentration was not significant. Contributions of the oil sands emissions to dry deposition fluxes of these species ranged from 3.8 to 13.1%. The precipitation-weighted mean concentrations of NO3-, SO42-, and NH4+ in samples with the oil sands sector were 76 %, 65 % and 81 % greater than those with the "Clean" sector, respectively. Contributions of the oil sands emissions to wet deposition of NO3-, SO42-, and NH4+ were 12.5 ± 8.9 %, 8.7 ± 4.4 %, and 6.0 ± 3.3 %, respectively. The annual total deposition of nitrogen and sulfur were 1.9 kg-N ha-1 and 0.74 kg-S ha-1, respectively, of which 8.0 ± 3.5 % and 8.7 ± 3.6 % were from oil sands emissions. The total deposition of sulfur and nitrogen did not exceed the critical loads (CL) of acidity, but nitrogen deposition exceeded the CLs of nutrient nitrogen in the region.

Cytocompatibility Evaluation of PEG-Methylsulfone Hydrogels.

Methylsulfone derivatized poly(ethylene) glycol (PEG) macromers can be biofunctionalized with thiolated ligands and cross-linked with thiol-based cross-linkers to obtain bioactive PEG hydrogels for in situ cell encapsulation. Methylsulfonyl-thiol (MS-SH) reactions present several advantages for this purpose when compared to other thiol-based cross-linking systems. They proceed with adequate and tunable kinetics for encapsulation, they reach a high conversion degree with good selectivity, and they generate stable reaction products. Our previous work demonstrated the cytocompatibility of cross-linked PEG-MS/thiol hydrogels in contact with fibroblasts. However, the cytocompatibility of the in situ MS-SH cross-linking reaction itself, which generates methylsulfinic acid as byproduct at the cross-linked site, remains to be evaluated. These studies are necessary to evaluate the potential of these systems for in vivo applications. Here we perform an extensive cytocompatibility study of PEG hydrogels during in situ cross-linking by the methylsulfonyl-thiol reaction. We compare these results with maleimide-thiol cross-linked PEGs which are well established for cell culture and in vivo experiments and do not involve the release of a byproduct. We show that fibroblasts and endothelial cells remain viable after in situ polymerization of methylsulfonyl-thiol gels on the top of the cell layers. Cell viability seems better than after in situ cross-linking hydrogels with maleimide-thiol chemistry. The endothelial cell proinflammatory phenotype is low and similar to the one obtained by the maleimide-thiol reaction. Finally, no activation of monocytes is observed. All in all, these results demonstrate that the methylsulfonyl-thiol chemistry is cytocompatible and does not trigger high pro-inflammatory responses in endothelial cells and monocytes. These results make methylsulfonyl-thiol chemistries eligible for in vivo testing and eventually clinical application in the future.

What Happens on Call Doesn't Stay on Call. The Effects of In-house Call on Acute Care Surgeons' Sleep and Burnout: Results of the Surgeon Performance (SuPer) Trial.

OBJECTIVE: We sought to quantify the effects of in-house call(IHC) on sleep patterns and burnout among acute care surgeons (ACS). BACKGROUND: Many ACS take INC, which leads to disrupted sleep and high levels of stress and burnout. METHODS: Physiological and survey data of 224 ACS with IHC were collected over 6 months. Participants continuously wore a physiological tracking device and responded to daily electronic surveys. Daily surveys captured work and life events as well as feelings of restfulness and burnout. The Maslach Burnout Inventory (MBI) was administered at the beginning and end of the study period. RESULTS: Physiological data were recorded for 34,135 days, which includes 4389 nights of IHC. Feelings of moderate, very, or extreme burnout occurred 25.7% of days and feelings of being moderately, slightly, or not at all rested occurred 75.91% of days. Decreased amount of time since the last IHC, reduced sleep duration, being on call, and having a bad outcome all contribute to greater feelings of daily burnout ( P <0.001). Decreased time since last call also exacerbates the negative effect of IHC on burnout ( P <0.01). CONCLUSIONS: ACS exhibit lower quality and reduced amount of sleep compared with an age-matched population. Furthermore, reduced sleep and decreased time since the last call led to increased feelings of daily burnout, accumulating in emotional exhaustion as measured on the MBI. A reevaluation of IHC requirements and patterns as well as identification of countermeasures to restore homeostatic wellness in ACS is essential to protect and optimize our workforce.

Interactions across the ages: How concerns about warmth and competence impact age-based stereotype threat in the workplace.

Although the disengagement consequences of age-based stereotype threat in the workplace are well-documented, it is less clear what causes employees to experience age-based stereotype threat. Based on socioemotional selectivity theory, the present study examines whether and why daily cross-age interactions in the workplace lead to stereotype threat. Using a diary study design over 2 weeks, 192 employees (86 employees aged 30 and younger; 106 employees aged 50 and older), completed 3570 reports on daily interactions with coworkers. Results showed that both younger and older employees experienced stereotype threat when they engaged in cross-age interactions compared to interactions with people of a similar age. The characteristics of cross-age interactions that led employees to experience stereotype threat differed by age, however. Consistent with socioemotional selectivity theory, cross-age interactions were problematic for younger employees to the degree that they triggered concerns about competence, whereas concerns about warmth led to stereotype threat among older employees. Daily stereotype threat was associated with reduced feelings of workplace belonging for both younger and older employees but, contrary to expectations, stereotype threat was not related to energy and stress. These findings suggest that cross-age interactions can lead to stereotype threat for both younger and older employees, particularly when younger employees worry they are perceived as incompetent or older employees worry they are perceived as less warm. (PsycInfo Database Record (c) 2023 APA, all rights reserved).

Dual Mating Strategies Observed in Male Clients of Female Sex Workers.

Humans have a complex and dynamic mating system, and there is evidence that our modern sexual preferences stem from evolutionary pressures. In the current paper we explore male use of a dual mating strategy: simultaneously pursuing both a long-term relationship (pair-bonding) as well as short-term, extra-pair copulations (variety-seeking). The primary constraint on such sexual pursuits is partner preferences, which can limit male behavior and hence cloud inferences about male preferences. The aim of this study was to investigate heterosexual male mating preferences when largely unconstrained by female partner preferences. In service of this goal, female full-service sex workers (N = 6) were surveyed on the traits and behaviors of their male clients (N = 516) and iterative cluster analysis was used to identify male mating typologies. Two clusters emerged: clients seeking a pair-bonding experience and clients seeking a variety experience. Results also suggested that romantically committed men were more likely to seek a variety experience than a relationship experience. We conclude that men desire both pair-bonding and sexual variety, and that their preference for one might be predicted by fulfilment of the other. These findings have implications for relationships, providing insight into motivations for male infidelity.

Gelation Kinetics and Mechanical Properties of Thiol-Tetrazole Methylsulfone Hydrogels Designed for Cell Encapsulation.

Hydrogel precursors that crosslink within minutes are essential for the development of cell encapsulation matrices and their implementation in automated systems. Such timescales allow sufficient mixing of cells and hydrogel precursors under low shear forces and the achievement of homogeneous networks and cell distributions in the 3D cell culture. The previous work showed that the thiol-tetrazole methylsulfone (TzMS) reaction crosslinks star-poly(ethylene glycol) (PEG) hydrogels within minutes at around physiological pH and can be accelerated or slowed down with small pH changes. The resulting hydrogels are cytocompatible and stable in cell culture conditions. Here, the gelation kinetics and mechanical properties of PEG-based hydrogels formed by thiol-TzMS crosslinking as a function of buffer, crosslinker structure and degree of TzMS functionality are reported. Crosslinkers of different architecture, length and chemical nature (PEG versus peptide) are tested, and degree of TzMS functionality is modified by inclusion of RGD cell-adhesive ligand, all at concentration ranges typically used in cell culture. These studies corroborate that thiol/PEG-4TzMS hydrogels show gelation times and stiffnesses that are suitable for 3D cell encapsulation and tunable through changes in hydrogel composition. The results of this study guide formulation of encapsulating hydrogels for manual and automated 3D cell culture.

Photoswitchable assembly of long-lived azobenzenes in water using visible light.

HYPOTHESIS: Switchable assemblies relevant for bio-applications may be accessed from water-soluble tetra-ortho-substituted azobenzenes that reversibly self-assemble and form complexes with ß-cyclodextrin under visible light. EXPERIMENTS: Two azobenzenes bearing either four fluorines or two chlorines and two fluorines in the ortho positions were synthesised with short poly(ethylene oxide) tails for water solubility. Photophysical properties were determined by UV-vis and 1H NMR spectroscopies, complexation with ß-cyclodextrin was assessed by 1H NMR spectroscopy, and self-assembly in water was investigated by static and dynamic light scattering. FINDINGS: Both molecules underwent trans-cis isomerization at 530 nm and cis-trans isomerization at 415 nm, with the cis forms exhibiting thermal half-lives > 300 days at room temperature. Both molecules formed inclusion complexes with ß-cyclodextrin in water, with cis-4F-AZO-PEO binding 3-fold stronger than trans, and 2Cl2F-AZO-PEO binding significantly weaker. Self-assembly of pure 2Cl2F-AZO-PEO in water showed an open association process regardless of configuration, while 4F-AZO-PEO showed an open association process for cis (Nagg increasing from 30 to 1000) but a closed association process for trans (Nagg stable at âˆ¼ 170). Aqueous solutions of 2Cl2F-AZO-PEO showed cloud points close to 45 °C, while the 4F-AZO-PEO isomers presented well-separated cloud points allowing reversible and all-visible transition between clear and turbid states at room temperature.

Benevolent Sexism and the Traditional Sexual Script as Predictors of Sexual Dissatisfaction in Heterosexual Women from the U.S.

Women report lower sexual satisfaction than men. Given that sexual dissatisfaction adversely impacts health and well-being, it is imperative that we investigate why women are sexually dissatisfied. In the present study, we explored whether women's benevolently sexist attitudes might predict their sexual dissatisfaction. In a sample of 308 (Mage = 38.09) heterosexual American women who had previously had sex with a man, we hypothesized that women's benevolent sexism would be associated with an increased adoption of the traditional sexual script (i.e., an increased propensity for submissiveness and passivity during sex) and that this, in turn, would be associated with increased sexual dissatisfaction. We also hypothesized that the relationship between the adoption of the traditional sexual script and sexual dissatisfaction would be moderated by the degree to which participants enjoy submissiveness. Overall, we did not find support for our model: benevolent sexism did not predict sexual dissatisfaction. However, we did find that adopting the traditional sexual script was predictive of sexual dissatisfaction for women who do not enjoy submissiveness. These findings contribute to an emerging literature pertaining to women's sexual health. Specifically, results suggest that benevolent sexism does not contribute to women's experiences of sexual dissatisfaction. Instead, they suggest that sexual dissatisfaction in women may (in part) be driven by their engagement in sexual roles that do not align with their sexual preferences. Theoretical and clinical implications for these findings are discussed.

Cross-national differences in willingness to believe conspiracy theories.

Conspiracy beliefs are not just generated by "under-the-skull" individual factors, but are shaped also by cultural, economic, and institutional realities. A scan of the literature-complemented by our own secondary data analyses-suggests a reasonable convergence of evidence that conspiracy beliefs are higher in nations that are more corrupt, more collectivist, and lower in GDP per capita. There is some evidence that conspiracy beliefs may also be shaped by economic inequality, power distance, and authoritarianism, although the evidence base is thin. We also review literature that examines how individual correlates of conspiracy beliefs vary across nations. We discuss challenges associated with conducting international research on conspiracy beliefs and chart a future research agenda for creating truly global insights into conspiracist thinking.

Thiol-Methylsulfone-Based Hydrogels for Cell Encapsulation: Reactivity Optimization of Aryl-Methylsulfone Substrate for Fine-Tunable Gelation Rate and Improved Stability.

Hydrogels are widely used as hydrated matrices for cell encapsulation in a number of applications, spanning from advanced 3D cultures and tissue models to cell-based therapeutics and tissue engineering. Hydrogel formation in the presence of living cells requires cross-linking reactions that proceed efficiently under close to physiological conditions. Recently, the nucleophilic aromatic substitution of phenyl-oxadiazole (Ox) methylsulfones (MS) by thiols was introduced as a new cross-linking reaction for cell encapsulation. Reported poly(ethylene glycol) (PEG)-based hydrogels featured tunable gelation times within seconds to a few minutes within pH 8.0 to 6.6 and allowed reasonably good mixing with cells. However, their rapid degradation prevented cell cultures to be maintained beyond 1 week. In this Article, we present the reactivity optimization of the heteroaromatic ring of the MS partner to slow down the cross-linking kinetics and the degradability of the derived hydrogels. New MS substrates based on phenyl-tetrazole (Tz) and benzothiazole (Bt) rings, with lower electrophilicity than Ox, were synthesized by simple pathways. When mixed with PEG-thiol, the novel PEG-MS extended the working time of precursor mixtures and allowed longer term cell culture. The Tz-based MS substrate was identified as the best candidate, as it is accessible by simple chemical reactions from cost-effective reactants, hydrogel precursors show good stability in aqueous solution and keep high chemoselectivity for thiols, and the derived Tz gels support cell cultures for >2 weeks. The Tz system also shows tunable gelation kinetics within seconds to hours and allows comfortable manipulation and cell encapsulation. Our findings expand the toolkit of thiol-mediated chemistry for the synthesis of hydrogels with improved properties for laboratory handling and future automatization.

A multivariate analysis of women's mating strategies and sexual selection on men's facial morphology.

The strength and direction of sexual selection via female choice on masculine facial traits in men is a paradox in human mate choice research. While masculinity may communicate benefits to women and offspring directly (i.e. resources) or indirectly (i.e. health), masculine men may be costly as long-term partners owing to lower paternal investment. Mating strategy theory suggests women's preferences for masculine traits are strongest when the costs associated with masculinity are reduced. This study takes a multivariate approach to testing whether women's mate preferences are context-dependent. Women (n = 919) rated attractiveness when considering long-term and short-term relationships for male faces varying in beardedness (clean-shaven and full beards) and facial masculinity (30% and 60% feminized, unmanipulated, 30% and 60% masculinized). Participants then completed scales measuring pathogen, sexual and moral disgust, disgust towards ectoparasites, reproductive ambition, self-perceived mate value and the facial hair in partners and fathers. In contrast to past research, we found no associations between pathogen disgust, self-perceived mate value or reproductive ambition and facial masculinity preferences. However, we found a significant positive association between moral disgust and preferences for masculine faces and bearded faces. Preferences for beards were lower among women with higher ectoparasite disgust, providing evidence for ectoparasite avoidance hypothesis. However, women reporting higher pathogen disgust gave higher attractiveness ratings for bearded faces than women reporting lower pathogen disgust, providing support for parasite-stress theories of sexual selection and mate choice. Preferences for beards were also highest among single and married women with the strongest reproductive ambition. Overall, our results reflect mixed associations between individual differences in mating strategies and women's mate preferences for masculine facial traits.

Reactive nano-patterns in triple structured bio-inspired honeycomb films as a clickable platform.

A hierarchically structured platform was obtained from directed self-assembly of a poly(styrene)-b-poly(4-vinylbenzylchloride) (PS-b-PVBC) block copolymer (BCP) during breath figure (BF) templating. The BF process using a water/ethanol atmosphere gave a unique double porosity in which hexagonally arranged micron-sized pores were encircled by a secondary population of smaller, nano-sized pores. A third level of structuration was simultaneously introduced between the pores by BCP self-assembly to form out-of-the-plane nano-cylinders, offering a film with an unprecedented triple structure, which could be used as a reactive platform. Indeed the surface nano-domains of VBC were exploited as reactive nano-patterns for site-specific chemical functionalization.

Design and Development of a Novel Upper-Limb Cycling Prosthesis.

The rise in popularity of the Paralympics in recent years has created a need for effective, low-cost sports-prosthetic devices for upper-limb amputees. There are various opportunities for lower-limb amputees to participate in cycling; however, there are only few options for those with upper-limb amputations. If the individual previously participated in cycling, a cycling-specific prosthesis could allow these activities to be integrated into rehabilitation methods. This article describes the processes involved with designing, developing and manufacturing such a prosthesis. The fundamental needs of people with upper-limb amputation were assessed and realised in the prototype of a transradial terminal device with two release mechanisms, including a sliding mechanism (for falls and minor collisions) and clamping mechanism (for head-on collisions). The sliding mechanism requires the rider to exert approximately 200 N, while the clamping mechanism requires about 700 N. The force ranges can be customised to match rider requirements. Experiments were conducted in a controlled environment to demonstrate stability of the device during normal cycling. Moreover, a volunteer test-rider was able to successfully activate the release mechanism during a simulated emergency scenario. The development of this prosthesis has the potential to enable traumatic upper-limb amputees to participate in cycling for rehabilitation or recreation.

Compliance with established guidelines for the radiological reporting of atypical femoral fractures.

OBJECTIVE: Atypical femoral fractures (AFFs) are important to diagnose early to avoid progression to complete fracture. We set out to determine the reporting accuracy of AFFs. METHODS: We conducted a retrospective analysis of imaging performed between November 2010 and June 2013 to analyse the X-ray reporting of AFFs and to describe the key clinical considerations. Radiological reports were reviewed from the 3805 separate femoral images for search terms thought likely to identify AFFs. This identified 1558 patients. The identified radiographs were reviewed by radiologists with reference to the 2010 American Society of Bone and Mineral Research (ASBMR) criteria. RESULTS: Within these 1558 patients, 16 patients met the radiological criteria for AFF according to the 2010 ASBMR task force statement of which, although all were identified as fractures, 15 were not reported as "atypical" by the original reporting author and none was formally classified as AFF by the original reporting author. Within the 1558 patients, there were an additional 17 patients labelled as having "atypical" fracture features originally, although only 1 patient met the 2010 ASBMR task force criteria for AFF. Only 13 of 16 patients had imaging of the contralateral femur, and there was a significant delay for those who were imaged (111 ± 44 days). Furthermore, two of the patients with an AFF had previous radiographs demonstrating cortical changes indicative of AFFs prior to formal diagnosis. CONCLUSION: Whilst AFFs are rare diagnoses, the compliance with published guidelines for their radiological classification is low. ADVANCES IN KNOWLEDGE: We have raised awareness of the importance of recognizing AFFs to guide management.

Effect of MacroRAFT Copolymer Adsorption on the Colloidal Stability of Layered Double Hydroxide Nanoparticles.

The colloidal behavior of layered double hydroxide nanoparticles containing Mg(2+) and Al(3+) ions as intralayer cations and nitrates as counterions (MgAl-NO3-LDH) was studied in the presence of a short statistical copolymer of acrylic acid (AA) and butyl acrylate (BA) terminated with 4-cyano-4-thiothiopropylsulfanyl pentanoic acid (CTPPA) (P(AA7.5-stat-BA7.5)-CTPPA) synthesized by reversible addition-fragmentation chain-transfer (RAFT) polymerization. Surface charge properties and aggregation of the particles were investigated by electrophoresis and dynamic light scattering (DLS), respectively. The negatively charged P(AA7.5-stat-BA7.5)-CTPPA adsorbed strongly on the oppositely charged particles, leading to charge neutralization at the isoelectric point (IEP) and charge reversal at higher copolymer concentrations. The dispersions were unstable, i.e., fast aggregation of the MgAl-NO3-LDH occurred near the IEP while high stability was achieved at higher P(AA7.5-stat-BA7.5)-CTPPA concentrations. Atomic force (AFM) and transmission electron (TEM) microscopy imaging revealed that the platelets preferentially adopted a face-to-face orientation in the aggregates. While the stability of the bare particles was very sensitive to ionic strength, the P(AA7.5-stat-BA7.5)-CTPPA copolymer-coated particles were extremely stable even at high salt levels. Accordingly, the limited colloidal stability of bare MgAl-NO3-LDH dispersions was significantly improved by adding an appropriate amount of P(AA7.5-stat-BA7.5)-CTPPA to the suspension.

Nanodiamonds with Surface Grafted Polymer Chains as Vehicles for Cell Imaging and Cisplatin Delivery: Enhancement of Cell Toxicity by POEGMEMA Coating.

Nanodiamonds (NDs) are highly promising drug carriers due to their biocompatibility, manipulable surface chemistry, and nonbleaching flourescence. In this communication, we compare the cytotoxicity of three ND-cisplatin systems in which cisplatin was incorporated via direct attachment to the ND surface, physical adsorption within a poly(oligo(ethylene glycol) methyl ether methacrylate) POEGMEMA surface coating, or complexation to 1,1-di-tert-butyl 3-(2-methacryloyloxy)ethyl)butane-1,1,3-tricarboxylate (MAETC) groups of a POEGMEMA-st-PMAETC surface layer. The polymer layers were introduced by grafting from RAFT-functionalized ND particles. All three ND systems displayed lower IC50 values than free cisplatin in A2870 and A2870cis ovarian cancer cells. The two polymer-containing systems outperformed their "naked" counterpart, with the POEGMEMA-coated particles the most cytotoxic, displaying an IC50 of 1.5 µM, more than an order of magnitude lower than that of cisplatin. The enhanced cytotoxicity is attributed to promotion of cellular uptake by the hydrophilic surface polymer.

Micelles based on gold-glycopolymer complexes as new chemotherapy drug delivery agents.

Polymeric versions of deacetylated auranofin, a gold complex with a sugar ligand, were prepared by post-modifying RAFT glycopolymers. Micellisation of a block copolymer containing pendant Au(I) units produced nanoparticles with an increased anti-proliferative effect against OVCAR-3 human ovarian carcinoma cells.