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Human exposure to mixtures of perfluoroalkyl and polyfluoroalkyl substances (PFASs) constitutes an important issue in environmental epidemiology and the adoption of more holistic approaches to reduce the uncertainties associated with their human health effects is a critical research need. The ‘exposome’, defined as the totality of environmental (i.e. nongenetic) exposures from conception onward represents a new path towards understanding environmental determinants of human disease by assessing the multitude of exposures and risk of adverse health outcomes that occur over a lifetime. Here, we review the limitations of traditional approaches to PFAS health assessments and explore how the exposome approach may be able to address such issues. We discuss the advantages and disadvantages of exposomic research and its implementation into human health studies, and provide suggestions for future research to adopt the exposome approach to better characterise the overall influence of PFAS exposures on human health.

Peripheral nerve injuries in which the nerve is not completely severed often result in neuromas-in-continuity. These can cause sensory and functional deficits and must be resected and reconstructed. In defects greater than 5 mm in length, nerve graft is indicated, and suture neurorrhaphy is typically used to secure the nerve ends. However, sutures may negatively impact nerve regeneration. Fibrin glue has recently been used to mitigate the inflammatory response associated with suture neurorrhaphy. Most of the literature regarding fibrin glue covers animal models and supports its use for nerve reconstruction. Tisseel, a fibrin sealant developed as an adjunct to hemostasis, has recently shown utility in peripheral nerve repair by increasing tensile strength without additional sutures. We present the successful use of Tisseel sealant in a neuroma resection and reconstruction. In this case, a 35-year-old female presented with persistent neuropathic pain and neurologic dysfunction related to the median nerve in her hand with a history of distal forearm laceration and prior carpal tunnel release. Upon exploration, a neuroma-in-continuity involving 75% of the nerve was identified, resected, and reconstructed using processed human nerve allograft, as well as Tisseel sealant and Axoguard nerve protector to secure the repair and offload tension. At 1-year follow-up, pain was resolved, with ≤8 mm static 2-point discrimination in the median nerve distribution, and excellent improvement in hand strength compared with preoperative conditions. The outcome of this case indicates that fibrin glue may be useful to avoid excess sutures in cases of neuroma-in-continuity not involving the entire cross-section of the nerve.

Adolescent males who have sex with males (AMSM) are at increased risk of HIV/STI acquisition compared to other adolescents, making sexual risk behaviors in this population a priority public health focus. AMSM experience more victimization (including sexual/partner violence), depression, and substance abuse than their heterosexual counterparts; these may form a syndemic associated with risky sexual behavior. We pooled data from the 2015 and 2017 Youth Risk Behavior Survey, restricted to male students who reported a previous male sexual partner (n = 448). Latent profile analysis was used to identify syndemic profiles, with log-binomial and cumulative complementary log–log models used to test associations with substance use at last intercourse, condomless sex at last intercourse, and the number of sexual partners. Nearly all measures of victimization, depression, and substance use had bivariate associations with greater substance use during sex and more sexual partners. We identified three profiles of AMSM: The profile (n = 55) with the greatest risk factors (evident of a syndemic) had substantially higher prevalence of substance use during sex (aPR = 4.74, 95% CI 3.02, 7.43) and more sexual partners (aPR = 2.45, 95% CI 1.39, 4.31) than the profile with the lowest risk factors (n = 326) after adjusting for confounders. This profile was not associated with condomless sex. We identified a syndemic characterized by victimization, depression, and substance use associated with risky sexual behaviors in a nationally representative sample of AMSM. Comprehensive sexual risk reduction interventions incorporating mental health and substance use are critically important in this population.

The presence of microplastics in the environment is substantially documented; however, the pathways of dietary exposure to microplastics are not yet well understood. This is the first study to document the presence of microplastics in bottled water sold in Australia from commercial outlets. In total, 16 brands of bottled water (Australian Sourced: n = 11, Imported: n = 5) sold in the two largest supermarkets in Australia were analysed in triplicate (n = 48) for the presence of polyethylene, PE; polystyrene, PS; polypropylene, PP; polyvinyl chloride, PVC; polyethylene terephthalate, PET; polycarbonate, PC; polymethylmethacrylate, PMMA; and polyamide, PA. Microplastics were detected in 94% (n = 15) of the samples, with PP (n = 14, 88%), PET (n = 10, 63%), PA (n = 7, 44%), and PE (n = 6, 38%) the most frequently detected. On average, a litre of bottled water contained 13 ± 19 (St Dev) microplastics, ranging from 0 to 80 microplastics/L. The average size of the microplastics identified in this study was 77 ± 22 μm. It was found that bottled water sourced and packaged overseas contained four times as many microplastics compared to bottled water sourced in Australia. It was estimated that in 2017, 28.3% of the Australian population consumed on average 30.8 L of bottled water; therefore, using the result from this study it is estimated that Australians are exposed to 400 microplastics annually through the consumption of bottled water. To understand the total amount of microplastics that Australians could be exposed to through dietary routes, further work is required to observe the presence of microplastics in other beverages and food.

A defining characteristic of bacterial cytochromes (cyt's) in the P460 family is an unusual cross-link connecting the heme porphyrin to the side chain of a lysyl residue in the protein backbone. Here, via proteomics of the periplasmic fraction of the ammonia-oxidizing bacterium (AOB) Nitrosomonas europaea, we report the identification of a variant member of the P460 family that contains a methionyl residue in place of the cross-linking lysine. We formally designate this protein cytochrome "c'β-Met" to distinguish it from other members bearing different residues at this position (e.g., cyt c'β-Phe from the methane-oxidizing Methylococcus capsulatus Bath). As isolated, the monoheme cyt c'β-Met is high-spin (S = 5/2). Optical spectroscopy suggests that a cross-link is absent. Hydroxylamine, the substrate for the cross-linked cyt P460 from N. europaea, did not appreciably alter the optical spectrum of cyt c'β with up to 1000-fold excess at pH 7.5. Cyt c'β-Met did however bind 1 equiv of H2O2, and with a slight excess, Mossbauer spectroscopy indicated the formation of a semistable ferryl (FeIV═O) Compound II-like species. The corresponding electron paramagnetic resonance showed a very low intensity signal indicative of a radical at g = 2.0. Furthermore, cyt c'β-Met exhibited guaiacol-dependent peroxidase activity (kcat = 20.0 ± 1.2 s-1; KM = 2.6 ± 0.4 mM). Unlike cyt c'β-Met, cyt P460 showed evidence of heme inactivation in the presence of 2 equiv of H2O2 with no appreciable guaiacol-dependent peroxidase activity. Mutagenesis of the cross-linking lysyl residue to an alanine in cyt P460, however, reversed this lack of activity.

Advances in analytical techniques have allowed greater detection of environmental contaminants from small volumes of sample. Four methodologies were evaluated for the extraction of 53 per- and polyfluoroalkyl substances (PFASs) from eight classes in 200 µL of avian and mammal serum. Spiked serums at four concentrations (0, 0.5, 5.0 and 25 ng mL−1) were prepared by protein precipitation (PPT), enhanced matrix removal (EMR), weak anion exchange (WAX), and hydrophilic-lipophilic balance (HLB) solid-phase extraction cartridges. The extract from each methodology was analysed by high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC–MS/MS), and concentrations were compared with known concentrations in the spiked media. EMR performed the best overall, with 40 of 53 compounds effectively recovered at 5 ng mL−1. Furthermore, EMR was effective overall at concentrations ranging from 0.5 to 25 ng mL−1 for 39 out of 53. Similarly, PPT was effective for 35 of 53 compounds at all spiked serum concentrations. There was a negative correlation between internal standard recovery for compounds with increasing octanol–water coefficients (Kow) for WAX (R = − 0.65, p = 0.0043) and HLB (R = − 0.62, p = 0.0077) extractions, indicating methanol may not be a suitable solvent for long-chain PFAS extraction from protein-rich tissues. EMR and PPT represent fast and effective methodologies for the extraction of PFASs from low volumes of serum which allows greater accuracy and precision that can be applied to future human and wildlife biomonitoring programmes.

Droughts in a warming climate have become more common and more extreme, making understanding forest responses to water stress increasingly pressing. Analysis of water stress in trees has long focused on water potential in xylem and leaves, which influences stomatal closure and water flow through the soil-plant-atmosphere continuum. At the same time, changes of vegetation water content (VWC) are linked to a range of tree responses, including fluxes of water and carbon, mortality, flammability, and more. Unlike water potential, which requires demanding in situ measurements, VWC can be retrieved from remote sensing measurements, particularly at microwave frequencies using radar and radiometry. Here, we highlight key frontiers through which VWC has the potential to significantly increase our understanding of forest responses to water stress. To validate remote sensing observations of VWC at landscape scale and to better relate them to data assimilation model parameters, we introduce an ecosystem-scale analog of the pressure–volume curve, the non-linear relationship between average leaf or branch water potential and water content commonly used in plant hydraulics. The sources of variability in these ecosystem-scale pressure-volume curves and their relationship to forest response to water stress are discussed. We further show to what extent diel, seasonal, and decadal dynamics of VWC reflect variations in different processes relating the tree response to water stress. VWC can also be used for inferring below-ground conditions—which are difficult to impossible to observe directly. Lastly, we discuss how a dedicated geostationary spaceborne observational system for VWC, when combined with existing datasets, can capture diel and seasonal water dynamics to advance the science and applications of global forest vulnerability to future droughts.

In 2018, over 30,000 L of fluorine-free firefighting foam was used to extinguish an industrial warehouse fire of uncharacterized chemical and industrial waste. Contaminated firewater and runoff were discharged to an adjacent freshwater creek in Melbourne, Australia. In this study, we applied nontarget analysis using liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QToF-MS) to 15 surface water samples to investigate the presence of legacy, novel and emerging per-and polyfluoroalkyl substances (PFAS). We identified six novel and emerging fluorotelomer-based fluorosurfactants in the Australian environment for the first time, including: fluorotelomer sulfonamido betaines (FTABs or FTSA-PrB), fluorotelomer thioether amido sulfonic acids (FTSASs), and fluorotelomer sulfonyl amido sulfonic acids (FTSAS-So). Legacy PFAS including C

Girls in foster care are at heightened risk for poor sexual health outcomes compared to their general population counterparts. Sexual minority girls are also at greater risk for poor sexual health compared to their heterosexual counterparts. Yet, little is known about the sexual health of sexual minority girls in foster care. This study aims to provide a preliminary understanding of how sexual minority girls in foster care experience the phenomenon of sexual health. Using a single-case interpretative phenomenological analysis (IPA) design, we interviewed five sexual minority girls in foster care using a single in-depth focus group discussion and analyzed the data using a series of IPA steps. Analysis revealed three major themes about the lived experiences of sexual health among sexual minority girls in foster care: fear of being victimized and distrust within sexual relationships, self-protection from sexual relationship harm, and sexual health communication. Further research is warranted to investigate the sexual health experiences and needs of sexual minority girls in foster care, with particular sensitivity to the potential impact of past sexual victimization and abuse on their sexual health and wellbeing.

PURPOSE: Racial/ethnic and sexual minorities experience numerous health disparities compared with their White and heterosexual counterparts, which may be exacerbated when these social identities intersect. The authors tested for differences in health care access and satisfaction across intersections of sexual identity and race/ethnicity. METHOD: A cross-sectional secondary data analysis of the 2012–2018 waves of the Association of American Medical Colleges biannual online Consumer Survey of Health Care Access was conducted. This survey captures a national sample of U.S. adults who reported needing health care in the past 12 months. The analytic sample included 29,628 participants. Sixteen possible combinations of sexual identity and race/ethnicity were examined. Health care access and satisfaction were measured with 10 items and an index created from these items. Cumulative prevalence ratios (PRs) for the index and PRs across sexual identity, both individually and in combination with race/ethnicity, for each health care access and satisfaction item were generated. RESULTS: Compared with White heterosexuals, all other groups had significantly more barriers to care before adjustment. The greatest barriers were observed among non-Hispanic Asian/Pacific Islander/Hawaiian gay/lesbian (unadjusted PR = 3.08; 95% confidence interval [CI]: 2.45, 3.88; adjusted PR = 2.01; 95% CI: 1.59, 2.53), non-Hispanic Black bisexual (unadjusted PR = 2.73; 95% CI: 2.28, 3.27; adjusted PR = 1.83; 95% CI: 1.52, 2.20), non-Hispanic Black other sexual identity (unadjusted PR = 2.27; 95% CI: 1.69, 3.06; adjusted PR = 2.07; 95% CI: 1.53, 2.78), and Hispanic/Latino other sexual identity (unadjusted PR = 2.06; 95% CI: 1.60, 2.65; adjusted PR = 1.39; 95% CI: 1.08, 1.79) participants. CONCLUSIONS: Persons of both racial/ethnic and sexual minority status generally had less health care access and satisfaction than White heterosexuals. An intersectional perspective is critical to achieving equity in quality health care access.

Semi‐arid forests need cost‐effective restoration strategies to address their severe degradation. Tree shelters are often used to minimize abiotic and biotic stress during seedling establishment. We asked if early‐successional weeds act as a natural shelter by facilitating native seedlings, contingent on abiotic and biotic stressors and seedling ecological strategy. We conducted a manipulative weed exclusion experiment at a semi‐arid site in South Texas targeted for large‐scale forest restoration to discern the net effect of weeds on the growth and survival of target thornscrub tree and shrub seedlings. We assessed the roles of contrasting seedling ecological strategies (fast vs. slow growth habit), temporal variation in abiotic stress, microclimate and mammalian herbivory in modulating weed–seedling interactions. Ungulate herbivory on seedlings was common, of similar frequency across most species, but not diminished by the presence of weed neighbours. On average, seedlings growing adjacent to weed neighbours experienced modest but non‐significant increases in both height and mortality after 6 months, relative to weed‐excluded areas. However, seedlings without significant herbivory and adjacent to weed neighbours grew more vigorously (increased height and branching) during hot and dry periods, particularly those species with a fast growth habit. Although seedling light‐saturated photosynthetic capacity (Asat) and air temperature were unaffected by weed presence during hot and dry periods, afternoon light levels were reduced by approximately 50%, possibly indicative of lower leaf temperatures and improved seedling water status. Our results show that realizing the facilitative potential of weeds in semi‐arid forest restoration requires minimizing mammalian herbivory and temporally separating competition for resources. Managing for intermediate but not excessive levels of forb canopy cover is likely required to reduce high radiation loads and reduce transpiration without adverse competitive effects. Longer‐term experiments manipulating cover crop identity, cover and mammalian herbivory will inform whether forbs can be effectively exploited to enhance restoration success at large scales.

Background Treatment of a child who has an anxiety disorder usually begins with the question of which treatment to start first, medication or psychotherapy. Both have strong empirical support, but few studies have compared their effectiveness head-to-head, and none has investigated what to do if the treatment tried first isn’t working well—whether to optimize the treatment already begun or to add the other treatment. Methods This is a single-blind Sequential Multiple Assignment Randomized Trial (SMART) of 24 weeks duration with two levels of randomization, one in each of two 12-week stages. In Stage 1, children will be randomized to fluoxetine or Coping Cat Cognitive Behavioral Therapy (CBT). In Stage 2, remitters will continue maintenance-level therapy with the single-modality treatment received in Stage 1. Non-remitters during the first 12 weeks of treatment will be randomized to either [1] optimization of their Stage 1 treatment, or [2] optimization of Stage 1 treatment and addition of the other intervention. After the 24-week trial, we will follow participants during open, naturalistic treatment to assess the durability of study treatment effects. Patients, 8–17 years of age who are diagnosed with an anxiety disorder, will be recruited and treated within 9 large clinical sites throughout greater Los Angeles. They will be predominantly underserved, ethnic minorities. The primary outcome measure will be the self-report score on the 41-item youth SCARED (Screen for Child Anxiety Related Disorders). An intent-to-treat analysis will compare youth randomized to fluoxetine first versus those randomized to CBT first (“Main Effect 1”). Then, among Stage 1 non-remitters, we will compare non-remitters randomized to optimization of their Stage 1 monotherapy versus non-remitters randomized to combination treatment (“Main Effect 2”). The interaction of these main effects will assess whether one of the 4 treatment sequences (CBT➔CBT; CBT➔med; med➔med; med➔CBT) in non-remitters is significantly better or worse than predicted from main effects alone. Discussion Findings from this SMART study will identify treatment sequences that optimize outcomes in ethnically diverse pediatric patients from underserved low- and middle-income households who have anxiety disorders. Trial registration This protocol, version 1.0, was registered in ClinicalTrials.gov on February 17, 2021 with Identifier: NCT04760275.

Few multifocal hand chondrosarcomas have been reported. To our knowledge, this report is the first to describe multifocal hand chondrosarcoma in a patient with no evidence of prior enchondroma, Ollier's disease, or Maffucci syndrome.

Terrestrial gross primary production (GPP) is the basis of vegetation growth and food production globally1 and plays a critical role in regulating atmospheric CO2 through its impact on ecosystem carbon balance. Even though higher CO2 concentrations in future decades can increase GPP2, low soil water availability, heat stress and disturbances associated with droughts could reduce the benefits of such CO2 fertilization. Here we analysed outputs of 13 Earth system models to show an increasingly stronger impact on GPP by extreme droughts than by mild and moderate droughts over the twenty-first century. Due to a dramatic increase in the frequency of extreme droughts, the magnitude of globally averaged reductions in GPP associated with extreme droughts was projected to be nearly tripled by the last quarter of this century (2075–2099) relative to that of the historical period (1850–1999) under both high and intermediate GHG emission scenarios. By contrast, the magnitude of GPP reductions associated with mild and moderate droughts was not projected to increase substantially. Our analysis indicates a high risk of extreme droughts to the global carbon cycle with atmospheric warming; however, this risk can be potentially mitigated by positive anomalies of GPP associated with favourable environmental conditions. Terrestrial primary productivity will increase with CO2 fertilization, but water limitation will decrease this positive effect. Analyses of Earth system model projections show that extreme droughts will have a much stronger impact on future productivity than mild and moderate droughts.

Background: Distal digital nerve repairs can present unique challenges for hand surgeons due to their sensitive location and ongoing difficulty obtaining soft tissue coverage in this region. Although autografts and nerve conduits have been shown to be of benefit with nerve gaps, they can have morbidities associated with their use. Nerve allografts have become a viable option over the past decade as their use has increased and data are now showing similar outcomes, particularly in short gap segments. Flaps and skin grafts are traditional coverage options for full thickness wounds but can pose challenges with multiple digit involvement, depth of wound, and critical structures exposed. Methods: We present a case where nerve allograft was used for distal digital nerve repair. Due to the distal nature of the nerve repair in the index digit distal to the trifurcation, the distal end of the nerve graft was connected to multiple small nerve ends. Dermal substitute was placed to achieve distal coverage of the affected digits. Results: At 6-month follow-up, the patient demonstrated improved strength, normal sensation, and full return of digital function. Conclusion: Nerve allograft can be used in combination with dermal skin substitute to achieve normal sensation and return of digital function following distal digital nerve injuries.

A quantitative method for the determination of per- and polyfluoroalkyl substances (PFAS) using liquid chromatography (LC) tandem mass spectrometry (MS/MS) was developed and applied to aqueous wastewater, surface water, and drinking water samples. Fifty-three PFAS from 14 compound classes (including many contaminants of emerging concern) were measured using a single analytical method. After solid-phase extraction using weak anion exchange cartridges, method detection limits in water ranged from 0.28 to 18 ng/L and method quantitation limits ranged from 0.35 to 26 ng/L. Method accuracy ranged from 70 to 127% for 49 of the 53 extracted PFAS, with the remaining four between 66 and 138%. Method precision ranged from 2 to 28% RSD, with 49 out of the 53 PFAS being below 20%. In addition to quantifying 50 PFAS, many of which are currently unregulated in the environment and not included in typical analytical lists, this method has efficiency advantages over other similar methods as it utilizes a single chromatographic separation with a shorter runtime (14 min), while maintaining method accuracy and stability and the separation of branched and linear PFAS isomers. The method was applied to wastewater influent and effluent; surface water from a river, wetland, and lake; and drinking water samples to survey PFAS contamination in Australian aqueous matrices. The compound classes FTCAs, FOSAAs, PFPAs, and diPAPs were detected for the first time in Australian WWTPs and the method was used to quantify PFAS concentrations from 0.60 to 193 ng/L. The range of compound classes detected and different PFAS signatures between sample locations demonstrate the need for expanded quantitation lists when investigating PFAS, especially newer classes in aqueous environmental samples. Graphical abstract.

We present a parameter estimation study of the Soil-Tree-Atmosphere Continuum (STAC) model, a process-based model that simulates water flow through an individual tree and its surrounding root zone. Parameters are estimated to optimize the model fit to observations of sap flux, stem water potential, and soil water storage made for a white fir (Abies concolor) in the Sierra Nevada, California. Bayesian inference is applied with a likelihood function that considers temporal correlation of the model errors. Key vegetation properties are estimated, such as the tree's root distribution, tolerance to drought, and hydraulic conductivity and retention functions. We find the model parameters are relatively non-identifiable when considering just soil water storage. Overall, by utilizing multiple processes (e.g. sap flow, stem water potential, and soil water storage) during the parameter estimation, we find the simulations of the soil and tree water properties to be more accurate when compared to observed data.

Contents Summary 1207 I. Introduction 1207 II. A brief history of modelling plant water fluxes 1208 III. Main components of plant water transport models 1208 IV. Stand-scale water fluxes and coupling to climate and soil 1213 V. Water fluxes in terrestrial biosphere models and feedbacks to community dynamics 1215 VI. Outstanding challenges in modelling water fluxes in the soil-plant-atmosphere continuum 1217 Acknowledgements 1218 References 1218 SUMMARY: Models of plant water fluxes have evolved from studies focussed on understanding the detailed structure and functioning of specific components of the soil-plant-atmosphere (SPA) continuum to architectures often incorporated inside eco-hydrological and terrestrial biosphere (TB) model schemes. We review here the historical evolution of this field, examine the basic structure of a simplified individual-based model of plant water transport, highlight selected applications for specific ecological problems and conclude by examining outstanding issues requiring further improvements in modelling vegetation water fluxes. We particularly emphasise issues related to the scaling from tissue-level traits to individual-based predictions of water transport, the representation of nonlinear and hysteretic behaviour in soil-xylem hydraulics and the need to incorporate knowledge of hydraulics within broader frameworks of plant ecological strategies and their consequences for predicting community demography and dynamics.

Sex bias in innate defense against Staphylococcus aureus skin and soft tissue infection (SSTI) is dependent on both estrogen production by the host and S. aureus secretion of the virulence factor, α-hemolysin (Hla). The impact of estrogen signaling on the immune system is most often studied in terms of the nuclear estrogen receptors ERα and ERβ. However, the potential contribution of the G protein-coupled estrogen receptor (GPER) to innate defense against infectious disease, particularly with respect to skin infection, has not been addressed. Using a murine model of SSTI, we found that GPER activation with the highly selective agonist G-1 limits S. aureus SSTI and Hla-mediated pathogenesis, effects that were absent in GPER knockout mice. Specifically, G-1 reduced Hla-mediated skin lesion formation and pro-inflammatory cytokine production, while increasing bacterial clearance. In vitro, G-1 reduced surface expression of the Hla receptor, ADAM10, in a human keratinocyte cell line and increased resistance to Hla-mediated permeability barrier disruption. This novel role for GPER activation in skin innate defense against infectious disease suggests that G-1 may have clinical utility in patients with epithelial permeability barrier dysfunction or who are otherwise at increased risk of S. aureus infection, including those with atopic dermatitis or cancer.

Woody plants vary in their adaptations to drought and shade. For a better prediction of vegetation responses to drought and shade within dynamic global vegetation models, it is critical to group species into functional types with similar adaptations. One of the key challenges is that the adaptations are generally determined by a large number of plant traits that may not be available for a large number of species. In this study, we present two heuristic woody plant groups that were separated using cluster analysis in a three-dimensional trait-environment space based on three key metrics for each species: mean xylem embolism resistance, shade tolerance and habitat aridity. The two heuristic groups separate these species into tolerators and avoiders. The tolerators either rely on their high embolism resistance to tolerate drought in arid habitats (e.g., Juniperus and Prunus) or rely on high shade tolerance to withstand shaded conditions in wet habitats (e.g., Picea, Abies and Acer). In contrast, all avoiders have low embolism resistance and low shade tolerance. In arid habitats, avoiders tend to minimize catastrophic embolism (e.g., most Pinus species) while in wet habitats, they may survive despite low shade tolerance (e.g., Betula, Populus, Alnus and Salix). Because our approach links traits to the environmental conditions, we expect it could be a promising framework for predicting changes in species composition, and therefore ecosystem function, under changing environmental conditions.

A systematic conceptual density functional theory (DFT) analysis was performed on a series of chlorinated chalcones to study the effect of electron distribution on antimicrobial activity. In our previous work, a series of 16 chlorinated chalcones were synthesized to determine the antimicrobial effects of varying the location of the halogen substituent on each aromatic ring of the chalcone. Herein is reported a DFT investigation of those 16 chalcones and a comparison of quantum chemical properties to their antimicrobial activity. DFT global chemical reactivity descriptors (chemical hardness/softness, chemical potential/electronegativity, and electrophilicity) and local reactivity descriptors (Fukui functions and dual descriptor) were calculated for all compounds using Spartan’18 software. All calculations were carried out at the B3LYP/6-31G* level of theory. Reactivity analysis of the Fukui dual descriptor calculations reveals sites of nucleophilic and electrophilic attack. These in-silico results provide a foundation for further synthetic optimization of the chalcone skeleton to serve as novel antimicrobial agents.

Herein is the first reported conceptual density functional theory (DFT) investigation of the purine alkaloid theacrine and the comparison of quantum chemical properties to the closely related stimulant caffeine. DFT global chemical reactivity descriptors (chemical hardness/softness, chemical potential/ electronegativity, and electrophilicity) and local reactivity descriptors (Fukui functions and dual descriptor) were calculated for both compounds using Spartan ‘16 software. All calculations were carried out at the B3LYP/6-31G* level of theory. Reactivity analysis of the Fukui dual descriptor calculations reveals sites of nucleophilic and electrophilic attack. The results provide a solid chemical foundation for understanding how theacrine interacts with cellular systems.

Glyphosate is currently the most widely used herbicide in the world, yet screening of environmental waters for this chemical is limited by the need for specialized derivatization and measurement methods that can be tedious and time-consuming. In this work, we present a novel method for the detection and quantification at trace levels of glyphosate and aminomethylphosphonic acid (AMPA) in environmental water samples. The detection and quantification of the analytes was performed by liquid chromatography (LC) coupled with tandem mass spectrometry (MS/MS). Chromatographic separation was achieved with an ion-exchange column and a pH-gradient elution of a solution of ammonium hydroxide and ammonium acetate. The limit of detection for glyphosate and AMPA was 0.25 μg L-1 and the limit of quantification was 0.5 μg L-1with a 20-μL injection. The method was used to investigate the levels of glyphosate and AMPA in surface water samples from the Yarra River catchment area and urban constructed stormwater wetlands. The results indicate that at the time of sampling, no glyphosate or AMPA was present in the samples from the Yarra River catchment area (n = 10). However, glyphosate was detected above the limit of quantification in 33% of the wetland samples (n = 12), with concentrations ranging from 1.95 to 2.96 μg L-1. Similarly, AMPA was quantified in 83% of the wetland samples, with concentrations ranging from 0.55 to 2.42 μg L-1. To our knowledge, this is the first report of a pH-gradient LC-MS/MS method for glyphosate and AMPA analysis at ultratrace levels, with minimal sample processing, avoiding costly, time-consuming derivatization and preconcentration steps. Graphical abstract ᅟ.

Introduction: We reported previously that when teams of students reflect on readings about communication, unconscious bias, and service-learning, their critical reflection, implicit bias mitigation, empathy, and compassionate behavior all increase. However, would these gains occur when intimate classroom settings, in-person team meetings, and direct interactions with people served were lost owing to the COVID-19 pandemic and remote learning? Methods: Before an online Medical Humanities course began in August 2020 and following the course in December 2020, 61 prospective medical students (54.1% female) completed reliable surveys of their reflective capacity (RC) and cognitive empathy (compassion). Students also completed surveys about their implicit biases and team community service in December 2020. Results: Both RC and empathy scores increased in students after they reflected on difficulties in communication, unconscious biases, and team service-learning experiences in the course. In written reflections, they reported how their compassionate behavior also grew owing to bias mitigation. Most students concurred that “unconscious bias might affect some of (their) clinical decisions or behaviors as a healthcare professional” and vowed to remain aware of these biases in clinical settings. Conclusions: Compared to previous years, the pandemic and remote learning had minimal effects on the benefits of our Medical Humanities course.

The role of disturbance in accelerating weed growth is well understood. While most studies have focused on soil mediated disturbance, mowing can also impact weed traits. Using silverleaf nightshade (Solanum elaeagnifolium), a noxious and invasive weed, through a series of field, laboratory, and greenhouse experiments, we asked whether continuous mowing influences growth and plant defense traits, expressed via different avenues, and whether they cascade into offspring. We found that mowed plants produced significantly less number of fruits, and less number of total seeds per plant, but had higher seed mass, and germinated more and faster. When three herbivores were allowed to feed, tobacco hornworm (Manduca sexta) caterpillars, gained more mass on seedlings from unmowed plants, while cow pea aphid (Aphis craccivora), a generalist, established better on mowed seedlings; however, leaf trichome density was higher on unmowed seedlings, suggesting possible negative cross talk in defense traits. Texas potato beetle (Leptinotarsa texana), a co-evolved specialist on S. elaeagnifolium, did not show any differential feeding effects. We also found that specific root length, an indicator of nutrient acquisition, was significantly higher in first generation seedlings from mowed plants. Taken together, we show that mowing is a selective pressure that enhances some fitness and defense traits and can contribute to producing superweeds.

Per-fluoroalkyl and polyfluoroalkyl substances (PFAS) are a diverse group of synthetic fluorinated chemicals used widely in industry and consumer products. Due to their extensive use and chemical stability, PFAS are ubiquitous environmental contaminants and as such, form an emerging risk factor for male reproductive health. The long half-lives of PFAS is of particular concern as the propensity to accumulate in biological systems prolong the time taken for excretion, taking years in many cases. Accordingly, there is mounting evidence supporting a negative association between PFAS exposure and an array of human health conditions. However, inconsistencies among epidemiological and experimental findings have hindered the ability to definitively link negative reproductive outcomes to specific PFAS exposure. This situation highlights the requirement for further investigation and the identification of reliable biological models that can inform health risks, allowing sensitive assessment of the spectrum of effects of PFAS exposure on humans. Here, we review the literature on the biological effects of PFAS exposure, with a specific focus on male reproduction, owing to its utility as a sentinel marker of general health. Indeed, male infertility has increasingly been shown to serve as an early indicator of a range of co-morbidities such as coronary, inflammatory, and metabolic diseases. It follows that adverse associations have been established between PFAS exposure and the incidence of testicular dysfunction, including pathologies such as testicular cancer and a reduction in semen quality. We also give consideration to the mechanisms that render the male reproductive tract vulnerable to PFAS mediated damage, and discuss novel remediation strategies to mitigate the negative impact of PFAS contamination and/or to ameliorate the PFAS load of exposed individuals.