1,950 results on '"B. Watson"'
Search Results
2. Evaluating Thin-Layer Sediment Placement as a Tool for Enhancing Tidal Marsh Resilience: a Coordinated Experiment Across Eight US National Estuarine Research Reserves
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Kenneth B. Raposa, Andrea Woolfolk, Charlie A. Endris, Monique C. Fountain, Gregg Moore, Megan Tyrrell, Rebecca Swerida, Scott Lerberg, Brandon J. Puckett, Matthew C. Ferner, Jeffrey Hollister, David M. Burdick, Lena Champlin, Johannes R. Krause, Dustin Haines, Andrew B. Gray, Elizabeth B. Watson, and Kerstin Wasson
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Ecology ,Aquatic Science ,Ecology, Evolution, Behavior and Systematics - Published
- 2023
3. Insights and Innovation: How a Local Public-Private Partnership is Building Home Care
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E. Ayn Welleford, Thelma B. Watson, Gigi Amateau, and Michelle Johnson
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Geriatrics and Gerontology ,Gerontology - Abstract
Recent national reports asserted an urgent imperative for transforming working conditions for the direct care workforce in the US. These clarion reports identified key influencers in reform as federal and state governments, workers’ unions and coalitions, individual and organizational employers. Equally essential and well-positioned local actors have been overlooked in the conversation—namely, municipalities, area agencies on aging, higher education, philanthropic entities, and community. Although deemed “essential,” direct care workers have been disproportionately affected by the COVID-19 pandemic. This paper examines an early public-private partnership initiative designed to recruit and train PCAs in Virginia.
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- 2023
4. Awareness and Knowledge of the Physical Activity Guidelines for Americans, 2nd Edition
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Tiffany J. Chen, Geoffrey P. Whitfield, Kathleen B. Watson, Janet E. Fulton, Emily N. Ussery, Eric T. Hyde, and Ken Rose
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Orthopedics and Sports Medicine - Abstract
Background: Assessing awareness and knowledge of the Physical Activity Guidelines for Americans, 2nd edition (Guidelines), released in 2018, is important for monitoring factors that contribute to increasing physical activity. Methods: We estimated prevalence of awareness and knowledge of the adult aerobic guideline (≥150 min/wk of moderate-intensity equivalent aerobic physical activity preferably spread out over a week) among adults (n = 3471) and of the youth aerobic guideline (≥60 min/d of mostly moderate- to vigorous-intensity aerobic physical activity) among a subset of parents (n = 744) from a nationwide sample of US adults in the 2019 FallStyles survey. We estimated odds ratios using logistic regression, adjusting for demographic and other characteristics. Results: Approximately 1 in 10 US adults and parents reported being aware of the Guidelines. Only 3% of adults knew the correct adult aerobic guideline. The most common responses were “don’t know/not sure” (44%) and “30 minutes a day, 5 or more days a week” (28%). Among parents, 15% knew the youth aerobic guideline. Awareness and knowledge tended to be lower with lower education and income. Conclusions: Limited awareness and knowledge of the Guidelines suggest communication about the Guidelines could be strengthened, especially among adults with low income or education.
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- 2023
5. Impact of resident involvement on complication rates in revision total knee arthroplasty
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Bradley, Alexander, Jared B, Watson, Kelly, Chandler, Mackenzie, Sowers, Gerald, McGwin, Nicola, Maffulli, Roshan, Jacob, and Sameer, Naranje
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General Medicine - Abstract
The number of revision total knee arthroplasty (TKA) procedures continues to rise, a direct consequence of the increase in primary TKA. The number of arthroplasty-trained orthopaedic surgeons has failed to increase at a corresponding rate, and the increased burden will ultimately fall on non-specialized orthopaedists. Resident involvement in primary TKA has not been found to increase postoperative complications, but revision TKA is more complex and the impact of resident involvement has not been well studied.Using the American College of Surgeons National Surgical Quality Improvement Program (ACS-NSQIP) database, this study identified 1834 revision TKA procedures between the years 2008 and 2012. Of these procedures, 863 included resident involvement. Demographic information, comorbidities, operative times, length of stay (LOS), and 30-day postoperative complications were stratified by resident and non-resident involvement and analyzed.Resident involvement was not associated with a significant increase in short-term complications. Operative times were significantly longer with resident involvement (147.50 min with resident involvement vs. 124.55 min without a resident, p 0.001). Length of stay after procedures with resident involvement was higher by 0.34 days, but this did not reach significance (p = 0.061).Resident involvement in revision total knee arthroplasty was associated with a significant increase in operative time; however, there were no significant increases in postoperative complication rates within 30 days. These findings support continued resident involvement in revision total knee arthroplasty cases and postoperative management.نتيجة لازدياد عدد عمليات تقويم مفصل الركبة، فإن عدد عمليات مراجعة تقويم مفصل الركبة مستمر في الارتفاع. لكن عدد جراحي العظام المدربين على تقويم المفاصل لم يواكب هذه الازدياد، وسيقع العبء المتزايد في النهاية على عاتق جراحي العظام غير المتخصصين. أظهرت الأبحاث أن مشاركة الأطباء المقيمين في عمليات تقويم مفصل الركبة الأولية لا ترتبط بزيادة مضاعفات ما بعد الجراحة، ولكن عمليات مراجعة تقويم مفصل الركبة أكثر تعقيدا ولم يتم دراسة تأثير مشاركة المقيمين بشكل جيد.باستخدام قاعدة بيانات البرنامج الوطني لتحسين جودة الجراحة بالكلية الأمريكية للجراحين، شملت هذه الدراسة 1834 عملية مراجعة تقويم مفصل الركبة أجريت بين عامي 2008 و 2012. من هذه العمليات، شارك الأطباء المقيمون في 863 عملية. تم تصنيف وتحليل المعلومات الديموغرافية، والأمراض المصاحبة، وأوقات الجراحة، ومدة الإقامة، ومضاعفات ما بعد الجراحة لمدة 30 يوما، حسب مشاركة الأطباء المقيمين.لم ترتبط مشاركة الأطباء المقيمين مع زيادة مهمة في المضاعفات على المدى القصير. كانت أوقات العمليات أطول بشكل ملحوظ مع مشاركة المقيمين (147.5 دقيقة مع مشاركة المقيمين مقابل 124.55 دقيقة بدون مقيم). كما كانت مدة الإقامة بعد الإجراءات بمشاركة المقيمين أعلى بمقدار 0.34 يوما، لكن هذا لم يصل إلى الأهمية الإحصائية.ارتبطت مشاركة المقيمين في مراجعة تقويم مفصل الركبة بزيادة كبيرة في وقت الجراحة. ومع ذلك، لم تكن هناك زيادة كبيرة في معدل المضاعفات بعد الجراحة في غضون 30 يوما. تدعم هذه النتائج استمرار مشاركة المقيمين في مراجعة حالات تقويم مفصل الركبة وإدارة ما بعد الجراحة.
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- 2022
6. The Relation Between Gendered Racial Microaggressions and Traumatic Stress Among Highly Educated Black Women
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Laurel B. Watson and Janee' Henderson
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Applied Psychology - Abstract
This study examined the relations among gendered racial microaggressions, resilience, individual and collective self-esteem, and traumatic stress among Black women. Personal self-esteem significantly mediated the positive relation between gendered racial microaggressions and traumatic stress. Resilience was also directly negatively related to traumatic stress and positively related to personal and collective self-esteem. Resilience moderated the positive relation between gendered racial microaggressions and membership identity/esteem. That is, at high levels of resilience, membership identity/esteem remained high, regardless of the frequency of gendered racial microaggressions. However, at low and average levels of resilience, membership identity/esteem was higher when experiencing more frequent gendered racial microaggressions. Mental health providers are encouraged to consider the deleterious role of gendered racial microaggressions in Black women’s traumatic stress. In addition, mental health providers should also consider the role of resilience in potentially mitigating traumatic stress and fostering Black women’s personal and collective self-esteem.
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- 2022
7. Does social media pay for music artists? Quantitative evidence on the co-evolution of social media, streaming and live music
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Allan Watson, Joseph B. Watson, and Lou Tompkins
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Cultural Studies - Published
- 2022
8. Multifaceted amelioration of cutaneous photoageing by (0.3%) retinol
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Kieran T. Mellody, Eleanor J. Bradley, Bezaleel Mambwe, Lindsay F. Cotterell, Orsolya Kiss, Poonam Halai, Zeena Loftus, Mike Bell, Tamara W. Griffiths, Christopher E. M. Griffiths, and Rachel E. B. Watson
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Aged, 80 and over ,Aging ,Pharmaceutical Science ,Dermatology ,Skin Aging ,Colloid and Surface Chemistry ,Chemistry (miscellaneous) ,Face ,Drug Discovery ,Humans ,Epidermis ,Vitamin A ,Aged ,Skin - Abstract
Although retinol skin care products improve the appearance of photoaged skin, there is a need for an effective retinol concentration that provides skin benefits without irritation.To compare the efficacy of topical 0.1%, 0.3% and 1% retinol in remodelling the cutaneous architecture in an in vivo experimental patch test study, and to determine tolerance of the most effective formulations when used in a daily in-use escalation study.For the patch test study, retinol products were applied under occlusion, to the extensor forearm of photoaged volunteers (n = 5; age range 66-84 years), and 3 mm skin biopsies obtained after 12 days. Effects of different retinol concentrations, and a vehicle control, on key epidermal and dermal biomarkers of cellular proliferation and dermal remodelling were compared to untreated baseline. Separately, participants (n = 218) recorded their tolerance to 0.3% or 1% retinol over a six-week, approved regimen, which gradually increased the facial applications to once nightly.Retinol treatment induced a stepwise increase in epidermal thickness and induced the expression of stratum corneum proteins, filaggrin and KPRP. 0.3% retinol and 1% retinol were comparably effective at inducing keratinocyte proliferation in the epidermis, whilst reducing e-cadherin expression. Fibrillin-rich microfibril deposition was increased following treatment with 0.3% and 1% retinol (p 0.01); other dermal components remained unaltered (e.g., fibronectin, collagen fibrils, elastin), and no evidence of local inflammation was detected. The in-use study found that 0.3% retinol was better tolerated than 1% retinol, with fewer and milder adverse events reported (χThis study suggests that 1% and 0.3% retinol concentrations were similarly effective at remodelling photodamaged skin in an in vivo model of long-term use. Use of 0.3% retinol in the escalation study was associated with fewer adverse reactions when applied daily. Hence, 0.3% retinol may be better tolerated than 1% retinol, thereby allowing longer-term topical application.Même si les produits de soins pour la peau à base de rétinol améliorent l'apparence de la peau photovieillie, il est nécessaire d'obtenir une concentration efficace de rétinol procurant des bénéfices cutanés sans irritation.Comparer l'efficacité du rétinol à 0.1%, 0.3% et 1% en application locale dans le remodelage de l'architecture cutanée dans une étude d'irritation cutanée in vivo expérimental, et déterminer la tolérance des formulations les plus efficaces lorsqu'elles sont utilisées dans une étude à doses progressives quotidiennes en cours d'utilisation. MÉTHODES: Pour l'étude d'irritation cutanée, des produits à base de rétinol ont été appliqués sous occlusion, sur le muscle extenseur de l'avant-bras de volontaires présentant des signes de photovieillissement (n = 5; tranche d'âge: 66 à 84 ans), et des biopsies cutanées de 3 mm ont été obtenues après 12 jours. Les effets des différentes concentrations de rétinol, et d'un véhicule témoin sur les principaux biomarqueurs épidermiques et dermiques de la prolifération cellulaire et du remodelage dermique ont été comparés à ceux observés à une région non traitée. Séparément, les participants (n = 218) ont enregistré leur tolérance au rétinol à 0.3% ou 1% au cours d'un schéma posologique approuvé de six semaines, qui a progressivement augmenté les applications faciales à une fois par nuit. RÉSULTATS: Le traitement par rétinol a induit une augmentation progressive de l'épaisseur épidermique, et a induit l'expression des protéines de la couche cornée, la filaggrine et le KPRP. Le rétinol à 0.3% et le rétinol à 1% étaient aussi efficaces pour induire la prolifération des kératinocytes dans l'épiderme, tout en réduisant l'expression de la cadhérine E. Le dépôt de microfibrilles riches en fibrilline a augmenté après un traitement par rétinol à 0.3% et 1% (p 0.001).Cette étude suggère que les concentrations de rétinol de 1% et 0.3% étaient aussi efficaces pour remodeler la peau photolésée dans un modèle in vivo lors d'une utilisation à long terme. L'utilisation de rétinol à 0.3% dans l'étude à doses progressives a été associée à moins d'effets indésirables lorsqu'il est appliqué quotidiennement. Par conséquent, le rétinol à 0.3% peut être mieux toléré que le rétinol à 1%, permettant ainsi une application topique à plus long terme.
- Published
- 2022
9. Mechanism of Visible Light-Mediated Alkene Aminoarylation with Arylsulfonylacetamides
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Anthony R. Allen, Jia-Fei Poon, Rory C. McAtee, Nicholas B. Watson, Derek A. Pratt, and Corey R.J. Stephenson
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General Chemistry ,Catalysis - Abstract
Alkene aminoarylation with arylsulfonylacetamides via a visible-light mediated radical Smiles-Truce rearrangement represents a convenient approach to the privileged arylethylamine pharmacaphore traditionally generated by circuitous, multi-step sequences. Herein, we report detailed synthetic, spectroscopic, kinetic, and computational studies designed to interrogate the proposed mechanism, including the key aryl transfer event. The data are consistent with a rate-limiting 1,4-aryl migration occurring either via a stepwise process involving a radical Meisenheimer-like intermediate or in a concerted fashion dependent on both arene electronics and alkene sterics. Our efforts to probe the mechanism have significantly expanded the substrate scope of the transformation with respect to the migrating aryl group and provide further credence to the synthetic potential of radical aryl migrations.
- Published
- 2023
10. Long-term and seasonal nitrate trends illustrate potential prevention of large cyanobacterial biomass by sediment oxidation in Hamilton Harbour, Lake Ontario
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Lewis A. Molot, David C. Depew, Arthur Zastepa, George B. Arhonditsis, Susan B. Watson, and Mark J. Verschoor
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Ecology ,Aquatic Science ,Ecology, Evolution, Behavior and Systematics - Published
- 2022
11. Chronic Conditions Among Adults Aged 18─34 Years — United States, 2019
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Kathleen B, Watson, Susan A, Carlson, Fleetwood, Loustalot, Machell, Town, Paul I, Eke, Craig W, Thomas, and Kurt J, Greenlund
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Adult ,Health (social science) ,Epidemiology ,Health, Toxicology and Mutagenesis ,Health Behavior ,General Medicine ,United States ,Health Risk Behaviors ,Behavioral Risk Factor Surveillance System ,Young Adult ,Risk-Taking ,Health Information Management ,Population Surveillance ,Chronic Disease ,Prevalence ,Humans - Abstract
Chronic conditions are common, costly, and major causes of death and disability.* Addressing chronic conditions and their determinants in young adulthood can help slow disease progression and improve well-being across the life course (1); however, recent prevalence estimates examining chronic conditions in young adults overall and by subgroup have not been reported. CDC analyzed data from the Behavioral Risk Factor Surveillance System (BRFSS) to measure prevalence of 11 chronic conditions among adults aged 18-34 years overall and by selected characteristics, and to measure prevalence of health-related risk behaviors by chronic condition status. In 2019, more than one half (53.8%) of adults aged 18-34 years reported having at least one chronic condition, and nearly one quarter (22.3%) reported having more than one chronic condition. The most prevalent conditions were obesity (25.5%), depression (21.3%), and high blood pressure (10.7%). Differences in the prevalence of having a chronic condition were most noticeable between young adults with a disability (75.8%) and without a disability (48.3%) and those who were unemployed (62.3%) and students (45.8%). Adults aged 18-34 years with a chronic condition were more likely than those without one to report binge drinking, smoking, or physical inactivity. Coordinated efforts by public and private sectors might help raise awareness of chronic conditions among young adults and help improve the availability of evidence-based interventions, policies, and programs that are effective in preventing, treating, and managing chronic conditions among young adults (1).
- Published
- 2022
12. Civilian Ballistic Femoral Shaft Fractures Compared With Blunt Femur Shaft Fractures
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David A. Patch, Eli B. Levitt, Nicholas A. Andrews, Alex R. Heatherly, Henry V. Bonner, Jared R. Halstrom, Jared B. Watson, and Clay A. Spitler
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Fractures, Open ,Treatment Outcome ,Humans ,Orthopedics and Sports Medicine ,Surgery ,Femur ,General Medicine ,Compartment Syndromes ,Femoral Fractures ,Fracture Fixation, Intramedullary ,Retrospective Studies - Abstract
To assess ballistic femoral shaft fracture outcomes in comparison with closed and open femoral shaft fractures sustained by blunt mechanisms. We hypothesized that ballistic femoral shaft fractures would have similar outcomes to blunt open fractures.Retrospective cohort study.Academic Level I trauma center.Patients 16 years and older presenting with ballistic (140), blunt closed (317), or blunt open (71) femoral shaft fractures.Unplanned return to operating room, fracture-related infection, soft tissue reconstruction, nonunion, implant failure, length of stay, Injury Severity Scores, hospital charges, and compartment syndrome.A total of 528 femoral shaft fractures were identified. A group of 140 ballistic fractures and comparison groups of all femoral shaft fractures sustained by blunt mechanisms and treated with intramedullary nailing were included in the analysis. Among the 2 subgroups of nonballistic injuries, 317 were blunt closed fractures and 71 were blunt open fractures. The ballistic group was associated with a 3-fold increase in overall complications (30%) compared with the blunt closed group (10%, P0.001), had a higher occurrence of thigh compartment syndrome (P0.001), and required more soft tissue reconstruction (P0.001) than either of the blunt fracture groups.Ballistic femoral shaft fractures do not perfectly fit with blunt closed or open femoral fractures. A high index of suspicion for the development of thigh compartment syndrome should be maintained in ballistic femoral shaft fractures. The overall rates of nonunion and infection were comparable between all groups, but the all-cause complication rate was significantly higher in the ballistic group compared with the blunt closed group.Prognostic Level III. See Instructions for Authors for a complete description of levels of evidence.
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- 2022
13. The Cost of Visibility: Minority Stress, Sexual Assault, and Traumatic Stress among Bisexual Women and Gender Expansive People
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Laurel B. Watson, Brandon Velez, Raquel S. Craney, and Sydney K. Greenwalt
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Cultural Studies ,Gender Studies - Published
- 2022
14. Evaluation of Vascular Repair by Tissue-Engineered Human Acellular Vessels or ePTFE Grafts in a Porcine Model of Limb Ischemia and Reperfusion
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Robert D. Kirkton, J. Devin B. Watson, Robert Houston, Heather L. Prichard, Laura E. Niklason, and Todd E. Rasmussen
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Surgery ,Critical Care and Intensive Care Medicine - Published
- 2023
15. Novel in-silico predicted matrikines are differential mediators of in vitro and in vivo cellular metabolism
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Nathan Jariwala, Matiss Ozols, Alexander Eckersley, Bezaleel Mambwe, Rachel E B Watson, Leo Zeef, Andrew Gilmore, Laurent Debelle, Mike Bell, Eleanor J Bradley, Yegor Doush, Carole Courage, Richard Leroux, Olivier Peschard, Philippe Mondon, Caroline Ringenbach, Laure Bernard, Aurelien Pitois, and Michael J Sherratt
- Abstract
SummaryThe exogenous application of small peptides can beneficially affect clinical skin appearance (wrinkles) and architecture (collagen and elastic fibre deposition and epidermal thickness). However, the discovery of new bioactive peptides has not been underpinned by any guiding hypothesis. As endogenous extracellular matrix (ECM)-derived peptides produced during tissue remodelling can act as molecular signals influencing cell metabolism, we hypothesised that protease cleavage site prediction could identify putative novel matrikines with beneficial activities. Here, we present anin silicotoin vivodiscovery pipeline, which enables the prediction and characterisation of peptide matrikines which differentially influence cellular metabolismin vitro. We use this pipeline to further characterise a combination of two novel ECM peptide mimics (GPKG and LSVD) which actin vitroto enhance the transcription of ECM organisation and cell proliferation genes andin vivoto promote epithelial and dermal remodelling. This pipeline approach can both identify new matrikines and provide insights into the mechanisms underpinning tissue homeostasis and repair.
- Published
- 2023
16. Ultraviolet radiation‐induced degradation of dermal extracellular matrix and protection by green tea catechins: a randomized controlled trial
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Nisamanee Charoenchon, Lesley E. Rhodes, Anna Nicolaou, Gary Williamson, Rachel E. B. Watson, and Mark D. Farrar
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Adult ,integumentary system ,Tea ,Ultraviolet Rays ,Humans ,Collagen ,Dermatology ,Catechin ,Extracellular Matrix ,Skin - Abstract
Loss and remodelling of the dermal extracellular matrix (ECM) are key features of photodamaged human skin. Green tea catechins (GTCs) have been explored for their anti-inflammatory and chemopreventive properties, but data on the impact of GTCs on ultraviolet radiation (UVR)-induced changes to the dermal ECM are lacking.To investigate the effect of an inflammatory dose of solar-simulated UVR on human dermal ECM and potential for protection by GTCs in a double-blind randomized controlled trial.In total, 50 healthy white (Fitzpatrick skin type I-II) adults aged 18-65 years were randomized to a combination of GTCs 540 mg plus vitamin C 50 mg or to placebo twice daily for 12 weeks. The impact of solar-simulated UVR at 3 × minimal erythema dose on the dermal collagen and elastic fibre networks was assessed by histology and immunohistochemistry in all participants at baseline. The impact of GTC supplementation on UVR-induced effects was compared between the groups post-supplementation.The area of papillary dermis covered by collagen and elastic fibres was significantly lower (P 0.001) in UVR-exposed skin than in unexposed skin. Significantly lower levels of fibrillin-rich microfibrils (P = 0.02), fibulin-2 (P 0.001) and fibulin-5 (P 0.001) were seen in UVR-exposed than unexposed skin, while procollagen-1 deposition was significantly higher in UVR-exposed skin (P = 0.01). Following GTC supplementation, the UVR-induced change in fibulin-5 was abrogated in the active group but not the placebo group, with no difference between the two groups for other components.Acute UVR induced significant changes in the human dermal collagen and elastic fibre networks, whereas oral GTCs conferred specific UVR protection to fibulin-5. Future studies could explore the impact of GTCs on the effects of repeated suberythemal UVR exposure of human skin.
- Published
- 2022
17. Geographic Differences in Sex-Specific Chronic Obstructive Pulmonary Disease Mortality Rate Trends Among Adults Aged ≥25 Years — United States, 1999–2019
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Susan A, Carlson, Anne G, Wheaton, Kathleen B, Watson, Yong, Liu, Janet B, Croft, and Kurt J, Greenlund
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Adult ,Male ,Rural Population ,Pulmonary Disease, Chronic Obstructive ,Health (social science) ,Urban Population ,Health Information Management ,Epidemiology ,Health, Toxicology and Mutagenesis ,Humans ,Female ,General Medicine ,United States - Abstract
Chronic obstructive pulmonary disease (COPD) accounts for the majority of deaths from chronic lower respiratory diseases, the fourth leading cause of death in the United States in 2019.* COPD mortality rates are decreasing overall. Although rates in men remain higher than those in women, declines have occurred among men but not women (1). To examine the geographic variation in sex-specific trends in age-adjusted COPD mortality rates among adults aged ≥25 years, CDC analyzed 1999-2019 death certificate data, by urban-rural status
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- 2022
18. Wound fluid sampling methods for proteomic studies: A scoping review
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Joe Harvey, Kieran T. Mellody, Nicky Cullum, Rachel E. B. Watson, and Jo Dumville
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Proteomics ,Wound Healing ,Drainage ,Humans ,Reproducibility of Results ,Surgery ,Dermatology - Abstract
Understanding why some wounds are hard to heal is important for improving care and developing more effective treatments. The method of sample collection used is an integral step in the research process and thus may affect the results obtained. The primary objective of this study was to summarise and map the methods currently used to sample wound fluid for protein profiling and analysis. Eligible studies were those that used a sampling method to collect wound fluid from any human wound for analysis of proteins. A search for eligible studies was performed using MEDLINE, Embase and CINAHL Plus in May 2020. All references were screened for eligibility by one reviewer, followed by discussion and consensus with a second reviewer. Quantitative data were mapped and visualised using appropriate software and summarised via a narrative summary. After screening, 280 studies were included in this review. The most commonly used group of wound fluid collection methods were vacuum, drainage or use of other external devices, with surgical wounds being the most common sample source. Other frequently used collection methods were extraction from absorbent materials, collection beneath an occlusive dressing and direct collection of wound fluid. This scoping review highlights the variety of methods used for wound fluid collection. Many studies had small sample sizes and short sample collection periods; these weaknesses have hampered the discovery and validation of novel biomarkers. Future research should aim to assess the reproducibility and feasibility of sampling and analytical methods for use in larger longitudinal studies.
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- 2022
19. Spatio-temporal connectivity of the aquatic microbiome associated with cyanobacterial blooms along a Great Lake riverine-lacustrine continuum
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Sophie Crevecoeur, Thomas A. Edge, Linet Cynthia Watson, Susan B. Watson, Charles W. Greer, Jan J. H. Ciborowski, Ngan Diep, Alice Dove, Kenneth G. Drouillard, Thijs Frenken, Robert Michael McKay, Arthur Zastepa, and Jérôme Comte
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Microbiology (medical) ,Microbiology - Abstract
Lake Erie is subject to recurring events of cyanobacterial harmful algal blooms (cHABs), but measures of nutrients and total phytoplankton biomass seem to be poor predictors of cHABs when taken individually. A more integrated approach at the watershed scale may improve our understanding of the conditions that lead to bloom formation, such as assessing the physico-chemical and biological factors that influence the lake microbial community, as well as identifying the linkages between Lake Erie and the surrounding watershed. Within the scope of the Government of Canada’s Genomics Research and Development Initiative (GRDI) Ecobiomics project, we used high-throughput sequencing of the 16S rRNA gene to characterize the spatio-temporal variability of the aquatic microbiome in the Thames River–Lake St. Clair-Detroit River–Lake Erie aquatic corridor. We found that the aquatic microbiome was structured along the flow path and influenced mainly by higher nutrient concentrations in the Thames River, and higher temperature and pH downstream in Lake St. Clair and Lake Erie. The same dominant bacterial phyla were detected along the water continuum, changing only in relative abundance. At finer taxonomical level, however, there was a clear shift in the cyanobacterial community, with Planktothrix dominating in the Thames River and Microcystis and Synechococcus in Lake St. Clair and Lake Erie. Mantel correlations highlighted the importance of geographic distance in shaping the microbial community structure. The fact that a high proportion of microbial sequences found in the Western Basin of Lake Erie were also identified in the Thames River, indicated a high degree of connectivity and dispersal within the system, where mass effect induced by passive transport play an important role in microbial community assembly. Nevertheless, some cyanobacterial amplicon sequence variants (ASVs) related to Microcystis, representing less than 0.1% of relative abundance in the upstream Thames River, became dominant in Lake St. Clair and Erie, suggesting selection of those ASVs based on the lake conditions. Their extremely low relative abundances in the Thames suggest additional sources are likely to contribute to the rapid development of summer and fall blooms in the Western Basin of Lake Erie. Collectively, these results, which can be applied to other watersheds, improve our understanding of the factors influencing aquatic microbial community assembly and provide new perspectives on how to better understand the occurrence of cHABs in Lake Erie and elsewhere.
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- 2023
20. Direct Chan–Lam Amination and Etherification of Aryl BMIDA Reagents
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John M. Halford‐McGuff, Eva M. Israel, Matthew J. West, Julien C. Vantourout, Allan J. B. Watson, The Leverhulme Trust, IBioIC, University of St Andrews. School of Chemistry, and University of St Andrews. Sir James Mackenzie Institute for Early Diagnosis
- Subjects
MCC ,Etherification ,Organic Chemistry ,Cross-coupling ,DAS ,QD ,Physical and Theoretical Chemistry ,QD Chemistry ,Copper ,Amination ,Boron - Abstract
Funding: Engineering and Physical Sciences Research Council; University of St Andrews; Leverhulme Trust (GrantNumber(s): RF-2022-014). We report the development of a method for the direct Chan–Lam coupling of arylboronic acid N-methyliminodiacetic acid esters (ArBMIDA) with amine and alcohol nucleophiles. A wide range of C–N and C–O cross-coupled products in 34–99% yield (34 examples). This method serves to expand the scope of organoboron components that can be used directly in this oxidative coupling reaction and provides opportunities for streamlining synthesis. Publisher PDF
- Published
- 2022
21. Copper(II) Fluoride
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Kane A.C. Bastick, Masakatsu Shibasaki, Allan J. B. Watson, and Motomu Kanai
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chemistry.chemical_compound ,Chemistry ,Copper(II) fluoride ,Nuclear chemistry - Published
- 2021
22. Walking and Other Common Physical Activities Among Adults with Arthritis — United States, 2019
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Dana Guglielmo, Louise B. Murphy, Kristina A. Theis, Michael A. Boring, Charles G. Helmick, Kathleen B. Watson, Lindsey M. Duca, Erica L. Odom, Yong Liu, and Janet B. Croft
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Adult ,Male ,Gerontology ,Health (social science) ,Adolescent ,Epidemiology ,Health, Toxicology and Mutagenesis ,Physical fitness ,Arthritis ,Walking ,Young Adult ,Quality of life (healthcare) ,Health Information Management ,Fibromyalgia ,Health care ,medicine ,Humans ,Full Report ,Exercise ,Aged ,Behavioral Risk Factor Surveillance System ,business.industry ,General Medicine ,Middle Aged ,medicine.disease ,Mental health ,United States ,Rheumatoid arthritis ,Female ,business - Abstract
The numerous health benefits of physical activity include reduced risk for chronic disease and improved mental health and quality of life (1). Physical activity can improve physical function and reduce pain and fall risk among adults with arthritis, a group of approximately 100 conditions affecting joints and surrounding tissues (most commonly osteoarthritis, fibromyalgia, gout, rheumatoid arthritis, and lupus) (1). Despite these benefits, the 54.6 million U.S. adults currently living with arthritis are generally less active than adults without arthritis, and only 36.2% of adults with arthritis are aerobically active (i.e., meet aerobic physical activity guidelines*) (2). Little is known about which physical activities adults with arthritis engage in. CDC analyzed 2019 Behavioral Risk Factor Surveillance System (BRFSS) data to examine the most common nonwork-related physical activities among adults with arthritis who reported any physical activity during the past month, nationally and by state. In 2019, 67.2% of adults with arthritis reported engaging in physical activity in the past month; among these persons, the most commonly reported activities were walking (70.8%), gardening (13.3%), and weightlifting (7.3%). In 45 U.S. states, at least two thirds of adults with arthritis who engaged in physical activity reported walking. Health care providers can help inactive adults with arthritis become active and, by encouraging physical activity and referring these persons to evidence-based physical activity programs, improve their health and quality of life.
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- 2021
23. Direct, Late‐Stage Mono‐ N ‐arylation of Pentamidine: Method Development, Mechanistic Insight, and Expedient Access to Novel Antiparastitics against Diamidine‐Resistant Parasites
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Glenn A. Burley, Harry P. de Koning, John Forsyth Russell Robertson, Katherine Louise Jones, Marzuq A. Ungogo, Leandro Lemgruber, Allan J. B. Watson, Mustafa M. Aldfer, Fergus S. McWhinnie, Bela E. Bode, University of St Andrews. School of Chemistry, University of St Andrews. Biomedical Sciences Research Complex, University of St Andrews. Centre of Magnetic Resonance, University of St Andrews. EaSTCHEM, and University of St Andrews. Sir James Mackenzie Institute for Early Diagnosis
- Subjects
Leishmania mexicana ,Amidines ,Drug Resistance ,Medicinal chemistry ,Biochemistry ,Amidine ,Structure-Activity Relationship ,chemistry.chemical_compound ,Drug Development ,Parasitic Sensitivity Tests ,Drug Discovery ,medicine ,QD ,General Pharmacology, Toxicology and Pharmaceutics ,Pentamidine ,Pharmacology ,Antiparasitic Agents ,Dose-Response Relationship, Drug ,Molecular Structure ,biology ,Chemistry ,Organic Chemistry ,Late stage ,DAS ,Leishmaniasis ,Arylation ,QD Chemistry ,medicine.disease ,biology.organism_classification ,Method development ,Antiparasitics ,Molecular Medicine ,Trypanosomiasis ,Copper ,DNA ,medicine.drug - Abstract
J.R. and G.A.B. thank GlaxoSmithKline (GSK) and the Engineering and Physical Sciences Research Council (EPSRC) for an industrial CASE studentship. MMA is supported by a studentship from the government of Libya, and MAU by a studentship from the Petroleum Technology Development Fund (PTDF), Abuja, Nigeria. A selective mono-N-arylation strategy of amidines under Chan-Lam conditions is described. During the reaction optimization phase, the isolation of a mononuclear Cu(II) complex provided unique mechanistic insight into the operation of Chan-Lam mono-N-arylation. The scope of the process is demonstrated, and then applied to access the first mono-N-arylated analogues of pentamidine. Sub-micromolar activity against kinetoplastid parasites was observed for several analogues with no cross-resistance in pentamidine and diminazene-resistant trypanosome strains and against Leishmania mexicana. A fluorescent mono-N-arylated pentamidine analogue revealed rapid cellular uptake, accumulating in parasite nuclei and the kinetoplasts. The DNA binding capability of the mono-N-arylated pentamidine series was confirmed by UV-melt measurements using AT-rich DNA. This work highlights the potential to use Chan-Lam mono-N-arylation to develop therapeutic leads against diamidine-resistant trypanosomiasis and leishmaniasis. Publisher PDF
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- 2021
24. Runnels mitigate marsh drowning in microtidal salt marshes
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Elizabeth B, Watson, Wenley, Ferguson, Lena K, Champlin, Jennifer D, White, Nick, Ernst, Habibata A, Sylla, Brittany P, Wilburn, and Cathleen, Wigand
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General Environmental Science - Abstract
As a symptom of accelerated sea level rise and historic impacts to tidal hydrology from agricultural and mosquito control activities, coastal marshes in the Northeastern U.S. are experiencing conversion to open water through edge loss, widening and headward erosion of tidal channels, and the formation and expansion of interior ponds. These interior ponds often form in high elevation marsh, confounding the notion applied in predictive modeling that salt marshes convert to open water when elevation falls below a critical surface inundation threshold. The installation of tidal channel extension features, or runnels, is a technique that has been implemented to reduce water levels and permit vegetation reestablishment in drowning coastal marshes, although there are limited data available to recommend its advisability. We report on 5 years of vegetation and hydrologic monitoring of two locations where a total of 600-m of shallow (0.15–0.30-m in diameter and depth) runnels were installed in 2015 and 2016 to enhance drainage, in the Pettaquamscutt River Estuary, in southern Rhode Island, United States. Results from this Before-After Control-Impact (BACI) designed study found that runnel installation successfully promoted plant recolonization, although runnels did not consistently promote increases in high marsh species presence or diversity. Runnels reduced the groundwater table (by 0.07–0.12 m), and at one location, the groundwater table experienced a 2-fold increase in the fraction of the in-channel tidal range that was observed in the marsh water table. We suggest that restoration of tidal hydrology through runnel installation holds promise as a tool to encourage revegetation and extend the lifespan of drowning coastal marshes where interior ponds are expanding. In addition, our study highlights the importance of considering the rising groundwater table as an important factor in marsh drowning due to expanding interior ponds found on the marsh platform.
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- 2022
25. Exploring Residents’ Perceptions of Neighborhood Development and Revitalization for Active Living Opportunities
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Nishita Dsouza, Natalicio Serrano, Kathleen B. Watson, Jean McMahon, Heather M. Devlin, Stephenie C. Lemon, Amy A. Eyler, Jeanette Gustat, and Jana A. Hirsch
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Adult ,Residence Characteristics ,Health Policy ,Racial Groups ,Ethnicity ,Public Health, Environmental and Occupational Health ,Humans ,Poverty ,Minority Groups - Abstract
Community fears of gentrification have created concerns about building active living infrastructure in neighborhoods with low-income populations. However, little empirical research exists related to these concerns. This work describes characteristics of residents who reported 1) concerns about increased cost of living caused by neighborhood development and 2) support for infrastructural improvements even if the changes lead to a higher cost of living.Data on concerns about or support for transportation-related and land use-related improvements and sociodemographic characteristics were obtained from the 2018 SummerStyles survey, an online panel survey conducted on a nationwide sample of US adults (n = 3,782). Descriptive statistics characterized the sample, and χOverall, 19.1% of study respondents agreed that development had caused concerns about higher cost of living. Approximately half (50.7%) supported neighborhood changes for active living opportunities even if they lead to higher costs of living. Prevalences of both concern and support were higher among respondents who were younger and who had higher levels of education than their counterparts. Support did not differ between racial or ethnic groups, but concern was reported more often by Hispanic/Latino (28.9%) and other non-Hispanic (including multiracial) respondents (25.5%) than by non-Hispanic White respondents (15.6%). Respondents who reported concerns were more likely to express support (65.3%) than respondents who did not report concerns (47.3%).The study showed that that low-income, racial, or ethnic minority populations support environmental changes to improve active living despite cost of living concerns associated with community revitalization.
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- 2022
26. Enhancing SLP Students' Perceptions of Older Persons and Collaborative Practice Through Geriatric Interprofessional Teamwork
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Teresa Drulia, Jennifer B. Watson, and Laurel Lynch
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Nursing ,Health professionals ,Perception ,media_common.quotation_subject ,Interprofessional teamwork ,Psychology ,media_common - Abstract
Purpose To address the need for practice-ready geriatric health professionals, the Seniors Assisting in Geriatric Education (SAGE) program was developed and implemented by two partnering institutions. This study examines speech-language pathology students' perceptions of interprofessional (IP) teamwork and older persons following participation in the SAGE program. Specifically, students reflected on their IP competencies and attitudes toward older persons and overall perceptions of their SAGE experience and how this experience may impact their future practice. Method IP teams of three or four students ( n = 662) from eight disciplines and two partnering institutions participated in the SAGE program. Over three semesters, IP student teams visited a senior mentor's home, completing assignments aimed at growing skills in geriatric collaborative care. A mixed-method approach was used to examine 20 speech-language pathology students' perceptions post-SAGE. Students completed two questionnaires and provided written and verbal feedback, including retrospective pre–post comparisons. Results Moderate positive effect sizes were observed on retrospective reports examining perceptions of IP knowledge, attitudes, and skills. These reports were consistent with responses to additional questions examining values/ethics, roles and responsibilities, IP communication, and teamwork. Quantitative and qualitative measures reflected predominantly positive attitudes toward older persons, including an appreciation for older adults, increased knowledge and skills in geriatric care, and an interest in working with older persons in the future. Conclusions Speech-language pathology students participating on an IP geriatric team reported improved knowledge, attitudes, and skills in geriatric collaborative care. Additional study is needed to determine the impact of this experience on students' behaviors as future IP team members.
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- 2021
27. Surveillance of Physical Activity and Sedentary Behavior Among Youth and Adults in the United States: History and Opportunities
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Emily N. Ussery, Susan A. Carlson, Geoffrey P. Whitfield, John D. Omura, Eric T. Hyde, Tiffany J. Chen, and Kathleen B. Watson
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Adult ,medicine.medical_specialty ,Adolescent ,Public health ,Health Behavior ,Physical activity ,Sedentary behavior ,United States ,Adolescent Behavior ,Surveys and Questionnaires ,Environmental health ,medicine ,Humans ,Orthopedics and Sports Medicine ,Public Health ,Sedentary Behavior ,Psychology ,Exercise ,Core function - Abstract
Background: Surveillance is a core function of public health, and approaches to national surveillance of physical activity and sedentary behavior have evolved over the past 2 decades. The purpose of this paper is to provide an overview of surveillance of physical activity and sedentary behavior in the United States over the past 2 decades, along with related challenges and emerging opportunities. Methods: The authors reviewed key national surveillance systems for the assessment of physical activity and sedentary behavior among youth and adults in the United States between 2000 and 2019. Results: Over the past 20 years, 8 surveillance systems have assessed physical activity, and 5 of those have assessed sedentary behavior. Three of the 8 originated in nonpublic health agencies. Most systems have assessed physical activity and sedentary behavior via surveys. However, survey questions varied over time within and also across systems, resulting in a wide array of available data. Conclusion: The evolving nature of physical activity surveillance in the United States has resulted in both broad challenges (eg, balancing content with survey space; providing data at the national, state, and local level; adapting traditional physical activity measures and survey designs; and addressing variation across surveillance systems) and related opportunities.
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- 2021
28. A New Decade of Healthy People: Considerations for Comparing Youth Physical Activity Across 2 Surveillance Systems
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Jessica J Minnaert, Shannon L. Michael, Susan A. Carlson, Kathleen B. Watson, Janet E. Fulton, and Tiffany J. Chen
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Adult ,medicine.medical_specialty ,Adolescent ,Demographics ,business.industry ,Public health ,Physical activity ,Odds ratio ,Guideline ,Youth Risk Behavior Survey ,Health Surveys ,Article ,Confidence interval ,Risk-Taking ,Adolescent Behavior ,Surveys and Questionnaires ,Proxy report ,medicine ,Humans ,Female ,Orthopedics and Sports Medicine ,Child ,business ,Exercise ,Demography - Abstract
Background: Healthy People 2030 includes objectives to increase meeting the aerobic physical activity guideline for ages 6–13 years (of ages 6–17 y, monitored by National Survey of Children’s Health [NSCH]) and grades 9 to 12 (mostly aged 14–18+ y, monitored by Youth Risk Behavior Survey [YRBS]). This study compares methodologies, prevalence, and patterns of meeting the guideline, particularly for overlapping ages 14–17 years. Methods: Nationally representative surveys, 2016–2017 NSCH (adult proxy report, 6–17 y) and 2015 and 2017 YRBS (self-report, grades 9–12), assess meeting the guideline of ≥60 minutes of daily moderate to vigorous physical activity. Prevalence and odds ratios were estimated by age group and demographics. Results: For youth aged 14–17 years, 17.4% (95% confidence interval [CI], 16.1–18.7; NSCH) and 27.0% (95% CI, 25.6–28.5; YRBS) met the guideline. 25.9% (95% CI, 24.8–27.2) aged 6–13 years (NSCH) and 26.6% (95% CI, 25.3–28.0) in grades 9 to 12 (YRBS) met the guideline. Across surveys, fewer females (P P Conclusions: Neither methodology nor estimates for meeting the aerobic guideline are similar across surveys, so age continuity between juxtaposed estimates should not be assumed by magnitude nor age for separate Healthy People 2030 youth physical activity objectives.
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- 2021
29. Trends in Aerobic and Muscle-Strengthening Physical Activity by Race/Ethnicity Across Income Levels Among US Adults, 1998–2018
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John D. Omura, Tiffany J. Chen, Kathleen B. Watson, Geoffrey P. Whitfield, and Eric T. Hyde
- Subjects
Adult ,medicine.medical_specialty ,business.industry ,Muscles ,Ethnic group ,Guideline ,Logistic regression ,Article ,Difference in differences ,Race (biology) ,Cross-Sectional Studies ,Epidemiology ,Ethnicity ,Income ,medicine ,Humans ,Aerobic exercise ,National Health Interview Survey ,Orthopedics and Sports Medicine ,business ,Exercise ,Minority Groups ,Demography - Abstract
Background: Although disparities in leisure-time physical activity (LTPA) participation by race/ethnicity and income are known, the combined association of these characteristics with LTPA participation is less understood. This study aims to describe trends and determine whether racial/ethnic differences in adult physical activity by income level have changed over the past 2 decades. Methods: The authors estimated LTPA participation (outcomes: any aerobic activity, meeting the aerobic activity guideline, meeting the muscle-strengthening guideline, and meeting the combined aerobic and muscle-strengthening guidelines) among adults ≥18 years by race/ethnicity across income levels using 1998–2018 National Health Interview Survey data in 3-year aggregates. They also tested for trends, prevalence differences, and difference in differences using logistic regression. Results: LTPA participation increased from 1998–2000 to 2016–2018 for all outcomes for non-Hispanic white, non-Hispanic black, and Hispanic adults at all income levels. Disparities narrowed for some groups but persisted between white and racial/ethnic minority groups across income levels for engaging in any aerobic activity and meeting the aerobic guideline (0.2–8.8 percentage point difference in differences). Disparities in meeting the muscle-strengthening and combined guidelines were less common. Conclusions: Opportunities exist to ensure that adults, particularly members of lower income racial/ethnic minority groups, have support to help them participate in LTPA.
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- 2021
30. Hydroxymethanesulfonate (HMS) Formation during Summertime Fog in an Arctic Oil Field
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Jason M. St. Clair, Paul O. Wennberg, Kerri A. Pratt, Thomas B. Watson, Jun Liu, John D. Crounse, Lu Xu, Claire E. Moffett, Rodney J. Weber, Qi Zhang, Rebecca J. Sheesley, Rime El Asmar, Michelle J. Kim, Matthew J. Gunsch, and Hannah M. Allen
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Oceanography ,Ecology ,Arctic ,Health, Toxicology and Mutagenesis ,Environmental Chemistry ,Environmental science ,Oil field ,Pollution ,Waste Management and Disposal ,Water Science and Technology - Abstract
Hydroxymethanesulfonate (HMS) is produced in the aqueous-phase reaction of formaldehyde (HCHO) and sulfur dioxide (SO₂) and has been proposed as a significant contributor to midlatitude wintertime pollution events. Here we report HMS detection within submicrometer atmospheric aerosols during frequent late summer, regional fog events in an Arctic oil field. The number fraction of individual particles containing HMS increased during fog periods, consistent with aqueous-phase formation. The single-particle mass spectra showed the primary particle signature (oil field emissions), plus secondary oxidized organics and sulfate, consistent with aqueous-phase processing. HMS mass concentrations ranged from below the ion chromatography limit of detection (0.3 ng/m³) to 1.6 ng/m³, with sulfate concentrations of 37–222 ng/m³. HCHO and SO₂ measurements suggest that the fog HMS production rate is ∼10 times higher in the oil fields than in the upwind Beaufort Sea. Aqueous-phase reactions of local oil field emissions during frequent summertime regional fog events likely have downwind impacts on Arctic aerosol composition. The potential for fog-based HMS production was estimated to be an order of magnitude higher in Fairbanks and Anchorage, AK, than in the oil fields and may explain the missing organosulfate source contributing to Fairbanks air quality.
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- 2021
31. Synthetic Approaches to the New Drugs Approved During 2020
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Andrew C. Flick, Carolyn A. Leverett, Hong X. Ding, Emma L. McInturff, Sarah J. Fink, Subham Mahapatra, Daniel W. Carney, Erick A. Lindsey, Jacob C. DeForest, Scott P. France, Simon Berritt, Simone V. Bigi-Botterill, Tony S. Gibson, Rebecca B. Watson, Yiyang Liu, and Christopher J. O’Donnell
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Immunoconjugates ,Drug Design ,Drug Discovery ,Molecular Medicine ,Humans - Abstract
New drugs introduced to the market are privileged structures that have affinities for biological targets implicated in human diseases and conditions. These new chemical entities (NCEs), particularly small molecules and antibody-drug conjugates (ADCs), provide insight into molecular recognition and simultaneously function as leads for the design of future medicines. This Review is part of a continuing series presenting the most likely process-scale synthetic approaches to 44 new chemical entities approved for the first time anywhere in the world during 2020.
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- 2022
32. Synthesis and Reactivity of (N2P2)Ni Complexes Stabilized by a Diphosphonite Pyridinophane Ligand
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Liviu M. Mirica, Nigam P. Rath, Giang N. Tran, Kei Fuchigami, and Michael B. Watson
- Subjects
Inorganic Chemistry ,chemistry.chemical_compound ,010405 organic chemistry ,Chemistry ,Ligand ,Phosphonite ,Organic Chemistry ,Reactivity (chemistry) ,Physical and Theoretical Chemistry ,010402 general chemistry ,01 natural sciences ,Medicinal chemistry ,0104 chemical sciences - Abstract
A series of (N2P2)NiII complexes (N2P2 = P,P′-ditertbutyl-2,11-diphosphonito[3.3](2,6)pyridinophane) stabilized by a modified tetradentate pyridinophane ligand containing two phosphonite groups wer...
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- 2021
33. 'I Was a Game or a Fetish Object': Diverse Bisexual Women’s Sexual Assault Experiences and Effects on Bisexual Identity
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Raquel S. Craney, Sydney K. Greenwalt, Cassandra Whitney, Marcella Beaumont, Mirella J. Flores, and Laurel B. Watson
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Cultural Studies ,Gender Studies ,Intersectionality ,Sexual minority ,Identity (social science) ,Qualitative content analysis ,Psychology ,Social psychology ,Expansive ,Object (philosophy) ,Minority stress ,Sexual assault - Abstract
Utilizing minority stress theory and intersectionality framework, this qualitative content analysis explored sexual assault experiences among 532 diverse bisexual women and gender expansive people....
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- 2021
34. Influence of landscape condition on relative abundance and body condition of two generalist freshwater turtle species
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Alissa L. Gulette, Brian E. Dickerson, James T. Anderson, Sara M. Crayton, Donald J. Brown, Joel L. Mota, Darien N. Lozon, Thomas K. Pauley, Mark B. Watson, Michael R. J. Forstner, Ivana Mali, and Danielle M. Canning
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0106 biological sciences ,Biodiversity ,Introduced species ,Generalist and specialist species ,010603 evolutionary biology ,01 natural sciences ,law.invention ,03 medical and health sciences ,law ,Abundance (ecology) ,Turtle (robot) ,Relative species abundance ,QH540-549.5 ,Ecology, Evolution, Behavior and Systematics ,Original Research ,Trachemys scripta elegans ,030304 developmental biology ,Nature and Landscape Conservation ,0303 health sciences ,Ecology ,biology ,habitat generalist ,Chrysemys picta ,land use ,biology.organism_classification ,Habitat ,Painted turtle - Abstract
Anthropogenic land use changes have broad impacts on biological diversity, often resulting in shifts in community composition. While many studies have documented negative impacts on occurrence and abundance of species, less attention has been given to native species that potentially benefit from anthropogenic land use changes. For many species reaching high densities in human‐dominated landscapes, it is unclear whether these environments represent higher quality habitat than more natural environments. We examined the influence of landscape ecological integrity on relative abundance and body condition of two native generalist freshwater turtle species that are prevalent in anthropogenic systems, the painted turtle (Chrysemys picta) and red‐eared slider (Trachemys scripta elegans). Relative abundance was negatively associated with ecological integrity for both species, but the relationship was not strongly supported for painted turtles. Body condition was positively associated with ecological integrity for painted turtles, with no strong association for red‐eared sliders. Our study suggests that both species benefitted at the population level from reduced ecological integrity, but individual‐level habitat quality was reduced for painted turtles. The differing responses between these two habitat generalists could partially explain why red‐eared sliders have become a widespread exotic invasive species, while painted turtles have not., Identifying the differences in the relationship between landscape integrity and body condition for painted turtles and red‐eared sliders may porovide insight on how red‐eared sliders have become a widespread invasive species, while painted turtles have not. We collected and collated turtle capture and morphometric data to create model‐estimated relationships between mean 2.5 km landscape condition value (LCV) and standardized body condition index (BCI) scores for (A) painted turtles (Chrysemys picta; n = 625) sampled at 46 wetlands across 10 counties in West Virginia and (B) red‐eared sliders (Trachemys scripta elegans; n = 715) sampled at 42 wetlands across five counties in Texas.
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- 2021
35. Drug-induced Hyperthermic Syndromes in Psychiatry
- Author
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Henry Rosenberg, Stanley N. Caroff, and Charles B. Watson
- Subjects
medicine.medical_specialty ,Antipsychotic agents ,Serotonin syndrome ,Review ,Malignant hyperthermia ,03 medical and health sciences ,Behavioral Neuroscience ,0302 clinical medicine ,Altered Mental Status ,medicine ,Genetic predisposition ,Pharmacology (medical) ,Induced hyperthermia ,Substance use disorders ,Intensive care medicine ,Adverse effect ,business.industry ,030208 emergency & critical care medicine ,medicine.disease ,Neuroleptic malignant syndrome ,Psychiatry and Mental health ,Psychotropic drug ,medicine.symptom ,business ,Rhabdomyolysis ,030217 neurology & neurosurgery - Abstract
Hyperthermia, or extreme elevations in body temperature, can be life-threatening and may be caused by prescription drugs or illegal substances acting at a number of different levels of the neuraxis. Several psychotropic drug classes and combinations have been associated with a classic clinical syndrome of hyperthermia, skeletal muscle hyper-metabolism, rigidity or rhabdomyolysis, autonomic dysfunction and altered mental status ranging from catatonic stupor to coma. It is critical for clinicians to have a high index of suspicion for these relatively uncommon drug-induced adverse effects and to become familiar with their management to prevent serious morbidity and mortality. Although these syndromes look alike, they are triggered by quite different mechanisms, and apart from the need to withdraw or restore potential triggering drugs and provide intensive medical care, specific treatments may vary. Clinical similarities have led to theoretical speculations about common mechanisms and shared genetic predispositions underlying these syndromes, suggesting that there may be a common "thermic stress syndrome" triggered in humans and animal models by a variety of pharmacological or environmental challenges.
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- 2021
36. Cu(OTf) 2 ‐Mediated Cross‐Coupling of Nitriles and N‐Heterocycles with Arylboronic Acids to Generate Nitrilium and Pyridinium Products**
- Author
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Nicola L. Bell, Thomas M. McGuire, Sonia Chabbra, Alexandra M. Z. Slawin, James W. B. Fyfe, David B. Cordes, Allan J. B. Watson, Chao Xu, Julien C. Vantourout, Bela E. Bode, Jeremy Brals, The Leverhulme Trust, EPSRC, University of St Andrews. Sir James Mackenzie Institute for Early Diagnosis, University of St Andrews. School of Chemistry, University of St Andrews. EaSTCHEM, University of St Andrews. Biomedical Sciences Research Complex, and University of St Andrews. Centre of Magnetic Resonance
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Reaction mechanism ,010402 general chemistry ,01 natural sciences ,Catalysis ,Reductive elimination ,chemistry.chemical_compound ,Transmetalation ,QD ,Nitrilium ,Boron ,010405 organic chemistry ,Aryl ,Cationic polymerization ,DAS ,General Medicine ,General Chemistry ,Arylation ,QD Chemistry ,Combinatorial chemistry ,0104 chemical sciences ,chemistry ,Covalent bond ,Cross-coupling ,Mechanism ,Pyridinium ,Copper - Abstract
Funding: Leverhulme Trust (Grant Number(s): RPG-2015-308), Leverhulme Trust (Grant Number(s): RPG-2018-362), Engineering and Physical Sciences Research Council (Grant Number(s): EP/R025754/1). Metal‐catalyzed C–N cross‐coupling generally forms C–N bonds by reductive elimination from metal complexes bearing covalent C‐ and N‐ligands. We have identified a Cu‐mediated C–N cross‐coupling that uses a dative N‐ligand in the bond forming event, which, in contrast to conventional methods, generates reactive cationic products. Mechanistic studies suggest the process operates via transmetalation of an aryl organoboron to a Cu(II) complex bearing neutral N‐ligands, such as nitriles or N‐heterocycles. Subsequent generation of a putative Cu(III) complex enables the oxidative C–N coupling to take place, delivering nitrilium intermediates and pyridinium products. The reaction is general for a range of N(sp) and N(sp2) precursors and can be applied to drug synthesis and late‐stage N‐arylation, and the limitations in the methodology are mechanistically evidenced. Publisher PDF
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- 2021
37. In Vivo Half-Life Extension of BMP1/TLL Metalloproteinase Inhibitors Using Small-Molecule Human Serum Albumin Binders
- Author
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Mark R. Harpel, Ghotas Evindar, Shenaz Bunally, David G. Washburn, Steve Wilson, Joanne Prendergast, Scott G. Summerfield, Katrina Rivera, Chun-wa Chung, Julien C. Vantourout, Steven R. Skinner, Neil Young, Xiaopeng Bai, Christopher C. Arico-Muendel, Albert Isidro-Llobet, Rakesh Lad, William Traylen, Graham L. Simpson, Josephine Yuen, Letian Kuai, Paul Scott-Stevens, Kim Lambert, Sandeep Pal, Saul Needle, Andrew M. Mason, Michael J Hobbs, Emma V. Edgar, Richard Snell, Lara S. Kallander, Eric X Shi, Lisa M. Shewchuk, Dennis A. Holt, and Allan J. B. Watson
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Biomedical Engineering ,Serum albumin ,Pharmaceutical Science ,Bioengineering ,Context (language use) ,Peptide ,02 engineering and technology ,Pharmacology ,01 natural sciences ,In vivo ,medicine ,chemistry.chemical_classification ,Metalloproteinase ,biology ,010405 organic chemistry ,Organic Chemistry ,021001 nanoscience & nanotechnology ,Human serum albumin ,Small molecule ,0104 chemical sciences ,chemistry ,biology.protein ,0210 nano-technology ,Biotechnology ,medicine.drug ,Conjugate - Abstract
Reducing the required frequence of drug dosing can improve the adherence of patients to chronic treatments. Hence, drugs with longer in vivo half-lives are highly desirable. One of the most promising approaches to extend the in vivo half-life of drugs is conjugation to human serum albumin (HSA). In this work, we describe the use of AlbuBinder 1, a small-molecule noncovalent HSA binder, to extend the in vivo half-life and pharmacology of small-molecule BMP1/TLL inhibitors in humanized mice (HSA KI/KI). A series of conjugates of AlbuBinder 1 with BMP1/TLL inhibitors were prepared. In particular, conjugate c showed good solubility and a half-life extension of >20-fold versus the parent molecule in the HSA KI/KI mice, reaching half-lives of >48 h with maintained maximal inhibition of plasma BMP1/TLL. The same conjugate showed a half-life of only 3 h in the wild-type mice, suggesting that the half-life extension was principally due to specific interactions with HSA. It is envisioned that conjugation to AlbuBinder 1 should be applicable to a wide range of small molecule or peptide drugs with short half-lives. In this context, AlbuBinders represent a viable alternative to existing half-life extension technologies.
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- 2021
38. Quantifying the uncertainties in multi-wavelength PAM fluorometry due to innate and irradiance-induced variability of fluorescence spectra
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Susan B. Watson, Laura Beecraft, and Ralph E. H. Smith
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0106 biological sciences ,010604 marine biology & hydrobiology ,Irradiance ,Soil science ,Aquatic Science ,010603 evolutionary biology ,01 natural sciences ,Fluorescence ,Photosynthetic capacity ,Fluorescence spectroscopy ,13. Climate action ,Fluorometer ,Calibration ,Environmental science ,Proxy (statistics) ,Relative species abundance ,Ecology, Evolution, Behavior and Systematics - Abstract
Multi-wavelength Chl a fluorometers are increasingly applied to assess phytoplankton photosynthetic capacity and composition, but their usefulness is limited by uncertainties in fluorescence excitation spectra (FES). We investigated this issue using the Phyto-PAM fluorometer to evaluate the effects of innate and irradiance-dependent variations in background (F) and variable (Fv) FES on analysis of three pigment groups (cyanobacteria, chlorophytes and chromophytes). The effects on group-specific estimates of minimum fluorescence (F0), a proxy for biomass, and Fv/Fm, the quantum yield of photochemistry, presented some challenges to the interpretation of group-specific results. F0 estimates usually had a 5–15% margin of error, even when measuring highly uneven mixtures, and applying imperfectly matched calibration FES or stressing samples with photosynthetically active and ultraviolet radiation; errors in Fv/Fm were commonly
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- 2021
39. Fully recyclable Brønsted acid catalyst systems
- Author
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Christopher B. Watson, Adrianna Kuechle, and David E. Bergbreiter
- Subjects
chemistry.chemical_classification ,Extraction (chemistry) ,Sulfonic acid ,Pollution ,Catalysis ,law.invention ,Solvent ,chemistry ,law ,Reagent ,By-product ,Environmental Chemistry ,Organic chemistry ,Brønsted–Lowry acid–base theory ,Distillation - Abstract
Homogeneous and heterogeneous sulfonic acid catalysts are some of the most common catalysts used in organic chemistry. This work explores an alternative scheme using a fully recyclable polymeric solvent (a poly-α-olefin (PAO)) and soluble PAO-anchored polyisobutylene (PIB)-bound sulfonic acid catalysts. This PAO solvent is nonvolatile and helps to exclude water by its nonpolar nature which in turn drives reactions without the need for distillation of water, avoiding the need for excess reagents. This highly nonpolar solvent system uses polyisobutylene (PIB) bound sulfonic acid catalysts that are phase-anchored in solvents like PAO. The effectivenes of these catalysts was demonstrated by their use in esterifications, acetalizations, and multicomponent condensations. These catalysts and the PAO solvent phase show excellent recyclability in schemes where products are efficiently separated. For example, this non-volatile polymeric solvent and the PIB-bound catalyst can be recycled quantitatively when volatile products are separated and purified by distillation. In other cases, product purification can be effected by product self-separation or by extraction.
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- 2021
40. Photoreductive chlorine elimination from a Ni(<scp>iii</scp>)Cl2 complex supported by a tetradentate pyridinophane ligand
- Author
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Liviu M. Mirica, Nigam P. Rath, Michael B. Watson, Hanah Na, and Fengzhi Tang
- Subjects
Chemistry ,Ligand ,Photodissociation ,Metals and Alloys ,chemistry.chemical_element ,General Chemistry ,Combinatorial chemistry ,Catalysis ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,Elimination reaction ,Materials Chemistry ,Ceramics and Composites ,Chlorine - Abstract
Herein we report the isolation, characterization, and photoreactivity of a stable NiIII dichloride complex supported by a tetradentate pyridinophane N-donor ligand. Upon irradiation, this complex undergoes an efficient photoreductive chlorine elimination reaction, both in solution and the solid-state. Subsequently, the NiIIICl2 species can be regenerated via a reaction with PhICl2.
- Published
- 2021
41. Preparation of Carbamates, Esters, Amides, and Unsymmetrical Ureas via Brønsted Acid-Activated N-Acyl Imidazoliums
- Author
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Jacob C. DeForest, Rebecca B. Watson, and Butler Todd W
- Subjects
Carbamate ,010405 organic chemistry ,Chemistry ,medicine.medical_treatment ,Organic Chemistry ,medicine ,Physical and Theoretical Chemistry ,010402 general chemistry ,Brønsted–Lowry acid–base theory ,human activities ,01 natural sciences ,Combinatorial chemistry ,0104 chemical sciences - Abstract
We report the application of Bronsted acid–activated N-acyl imidazoliums as versatile intermediates in carbonyl transformations. The efficient and scalable procedure was validated on a diverse set ...
- Published
- 2020
42. Methane and nitrous oxide measured throughout Lake Erie over all seasons indicate highest emissions from the eutrophic Western Basin
- Author
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Susan B. Watson, Jay A. Brandes, Arthur Zastepa, J. Fernandez, and Amy Townsend-Small
- Subjects
geography ,geography.geographical_feature_category ,Ecology ,business.industry ,Global warming ,Aquatic Science ,Atmospheric sciences ,Sink (geography) ,Methane ,chemistry.chemical_compound ,chemistry ,Natural gas ,Greenhouse gas ,Phytoplankton ,Environmental science ,business ,Tonne ,Eutrophication ,Ecology, Evolution, Behavior and Systematics - Abstract
Eutrophication has been linked to increased greenhouse gas emissions from inland waters. Phytoplankton blooms in Lake Erie have increased since the 1990s, although its greenhouse gas emissions are not well characterized. We measured CH4 and N2O concentrations and diffusive fluxes in four seasons around the entire lake, and CO2 fluxes in one summer season. Lake Erie is a source of CH4 all year across the lake, concentrated in spring and summer in the Western Basin. Methane emissions ranged from 0.03 to 14.87 mg C m−2 d-1. Methane is predominantly biogenic, and natural gas leaks are an insignificant source. While Lake Erie is an overall N2O source, it is an N2O sink in winter and occasionally during summer. Emissions of N2O ranged from −0.08 to 1.22 mg N m−2 d-1. We also measured CO2 fluxes in summer only, when Lake Erie is a small atmospheric CO2 sink. While areal fluxes of CH4 and N2O are similar to those observed elsewhere, total fluxes from Lake Erie are higher due to its surface area. Lake Erie emits ~ 6300 (±19%) metric tons of CH4-C yr−1 and ~600 (±37%) metric tons N2O-N yr−1: almost 500,000 metric tons CO2-eq yr−1 total. This is the first comprehensive dataset of CH4 and N2O concentrations and diffusive emissions in a very large lake. More measurements and monitoring are needed to determine whether increased eutrophication in the Great Lakes is tied to increased emissions of these powerful climate forcers in a possible positive feedback to climate warming.
- Published
- 2020
43. Awareness And Knowledge Of The 2018 Physical Activity Guidelines Among US Adults
- Author
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Tiffany J. Chen, Geoffrey P. Whitfield, Emily N. Ussery, Kathleen B. Watson, Eric T. Hyde, Janet E. Fulton, and Ken Rose
- Subjects
Physical Therapy, Sports Therapy and Rehabilitation ,Orthopedics and Sports Medicine - Published
- 2022
44. Relationships between ecosystem properties and sea-level rise vulnerability of tidal wetlands of the U.S. Mid-Atlantic
- Author
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Tracy Elsey-Quirk, Elizabeth B. Watson, Kirk Raper, Danielle Kreeger, Bhanu Paudel, LeeAnn Haaf, Martha Maxwell-Doyle, Angela Padeletti, Erin Reilly, and David J. Velinsky
- Subjects
Wetlands ,General Medicine ,Mid-Atlantic Region ,Sea Level Rise ,Management, Monitoring, Policy and Law ,Estuaries ,Pollution ,Ecosystem ,Environmental Monitoring ,General Environmental Science - Abstract
Tidal wetlands in the Mid-Atlantic, USA, are experiencing high rates of relative sea level rise, and it is unclear whether they will be resilient in the face of future flooding increases. In a previous study, we found 80% of our study areas in tidal freshwater and salt marshes in the Delaware Estuary and Barnegat Bay had elevation change rates lower than the 19-year increase in mean sea level. Here, we examine relationships between marsh elevation dynamics and abiotic and biotic parameters in order to assess their utility as indicators of vulnerability to relative sea level rise. We further apply a range of marsh vulnerability indicators including elevation change rates to evaluate their ability to corroborate marsh habitat change over the last 30 years. Of the field measurements, soil bulk density and belowground plant biomass were among the strongest predictors of elevation change and accretion dynamics across all marsh types and settings. Both tidal freshwater and salt marshes tended to have higher rates of elevation increase and surface accretion in areas where soil bulk density and live belowground biomass were higher. Nine of the ten marshes experienced a net loss of area from the 1970s to 2015 ranging from 0.05 to 14%. Although tidal freshwater marshes were low in elevation and experienced variable elevation change rates, marsh area loss was low. Conversely, salt marshes closest to the coast and perched high in the tidal frame with a higher degree of human modification tended to experience the greatest marsh loss, which incorporated anthropogenic impacts and edge erosion. Thus, our regional assessment points to the need for a comprehensive understanding of factors that influence marsh resilience including human modifications and geomorphic settings.
- Published
- 2022
45. The solubility of titanite in silicate melt determined from growth and dissolution experiments
- Author
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John C. Ayers, Daniel Flanagan, Calvin Miller, E. B. Watson, F. J. Ryerson, Blake Wallrich, and Michael Ackerson
- Subjects
Geophysics ,Geochemistry and Petrology - Published
- 2022
46. Academic achievement with cooperative learning using homogeneous and heterogeneous groups
- Author
-
Patricia J. Wyman and Scott B. Watson
- Subjects
Cooperative learning ,Mathematics (miscellaneous) ,History and Philosophy of Science ,Physics and Astronomy (miscellaneous) ,Homogeneous ,Mathematics education ,Academic achievement ,Psychology ,Engineering (miscellaneous) ,Education - Published
- 2020
47. Bisexual Women: Experiencing and Coping with Objectification, Prejudice, and Erasure
- Author
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Laurel B. Watson, Kelly Lamkins, Chris Brown, Christine R. Serpe, and Shawnalee Criss
- Subjects
Cultural Studies ,050103 clinical psychology ,Coping (psychology) ,030505 public health ,05 social sciences ,Gender Studies ,03 medical and health sciences ,0501 psychology and cognitive sciences ,Objectification ,Lesbian ,Sexual objectification ,0305 other medical science ,Psychology ,Social psychology ,Qualitative research - Abstract
Fredrickson and Roberts’ sexual objectification theory has been successfully tested across sexually diverse groups (e.g., heterosexual, lesbian). However, objectification theory research has rarely...
- Published
- 2020
48. Superelectrophilic aluminium(iii)–ion pairs promote a distinct reaction path for carbonyl–olefin ring-closing metathesis
- Author
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Jessica L. Gomez-Lopez, Rebecca B. Watson, Ashlee J. Davis, Corinna S. Schindler, and Daniel J. Nasrallah
- Subjects
Reaction mechanism ,Olefin fiber ,Process Chemistry and Technology ,chemistry.chemical_element ,Bioengineering ,Metathesis ,Biochemistry ,Combinatorial chemistry ,Chemical synthesis ,Catalysis ,Ring-closing metathesis ,chemistry ,Aluminium ,Salt metathesis reaction - Abstract
Catalytic carbonyl–olefin metathesis reactions represent powerful synthetic strategies for alkene formation. Successful approaches for carbonyl–olefin ring-closing, ring-opening and cross metathesis have been developed in recent years, but current limitations hamper the generality of these transformations. Stronger, more efficient catalytic systems are needed to further broaden the scope of these transformations while they prevent undesired reaction pathways. Here we report the development of an aluminium-based heterobimetallic ion pair as a superior catalyst that promotes carbonyl–olefin ring-closing metathesis via a distinct reaction mechanism and allows access to six- and seven-membered rings, which suffer from low yields and poor conversion under previously reported conditions. Mechanistic investigations support a distinct reaction profile in which two productive reaction pathways competitively form metathesis products. These insights are expected to have important implications in the catalyst design and development for carbonyl–olefin metathesis and enable future advances to ultimately expand the synthetic utility of these transformations. Carbonyl–olefin metathesis reactions are a valuable tool in synthetic chemistry, but there are still some limitations in scope. Now, a catalyst system allows the activation of previously unreactive substrates for such a reaction by aluminium(iii)–ion pairs acting as Lewis acidic superelectrophiles.
- Published
- 2020
49. Mechanisms underlying the enhancement of γ‐aminobutyric acid responses in the external globus pallidus of R6/2 Huntington’s disease model mice
- Author
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Joseph B. Watson, Carlos Cepeda, Michael Levine, Joshua Barry, and Theodore A. Sarafian
- Subjects
Male ,0301 basic medicine ,GABA Plasma Membrane Transport Proteins ,medicine.medical_specialty ,Genotype ,Stimulation ,Striatum ,GABAB receptor ,Globus Pallidus ,Indirect pathway of movement ,Aminobutyric acid ,Article ,GABA Antagonists ,Mice ,03 medical and health sciences ,Cellular and Molecular Neuroscience ,0302 clinical medicine ,Huntington's disease ,Internal medicine ,medicine ,Animals ,GABA transporter ,GABA-A Receptor Antagonists ,gamma-Aminobutyric Acid ,biology ,Chemistry ,Antagonist ,medicine.disease ,Immunohistochemistry ,Electrophysiological Phenomena ,Mice, Inbred C57BL ,Optogenetics ,Disease Models, Animal ,Huntington Disease ,030104 developmental biology ,Endocrinology ,nervous system ,biology.protein ,Female ,030217 neurology & neurosurgery - Abstract
In Huntington's disease (HD), the output of striatal indirect pathway medium-sized spiny neurons (MSNs) is altered in its target region, the external globus pallidus (GPe). In a previous study we demonstrated that selective optogenetic stimulation of indirect pathway MSNs induced prolonged decay time of γ-aminobutyric acid (GABA) responses in GPe neurons. Here we identified the mechanism underlying this alteration. Electrophysiological recordings in slices from symptomatic R6/2 and wildtype (WT) mice were used to evaluate, primarily, the effects of GABA transporter (GAT) antagonists on responses evoked by optogenetic activation of indirect pathway MSNs. In addition, immunohistochemistry (IHC) and Western blots (WBs) were used to examine GAT-3 expression in HD and WT mice. A GAT-3 blocker (SNAP5114) increased decay time of GABA responses in WT and HD GPe neurons, but the effect was significantly greater in WT neurons. In contrast, a GAT-1 antagonist (NO-711) or a GABAB receptor antagonist (CGP 54626) produced small increases in decay time but no differential effects between genotypes. IHC and WBs showed reduction of GAT-3 expression in the GPe of HD mice. Thus, reduced expression or dysfunction of GAT-3 could underlie alterations of GPe responses to GABA inputs from striatum and could be a target for therapeutic intervention.
- Published
- 2020
50. Catalytic Enantioselective Synthesis of Heterocyclic Vicinal Fluoroamines by Using Asymmetric Protonation: Method Development and Mechanistic Study
- Author
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Allan J. B. Watson, Andrew R. Leach, Alexandra M. Z. Slawin, Cameron L. Carpenter-Warren, Matthew Ashford, John J. Molloy, Chao Xu, The Leverhulme Trust, University of St Andrews. Sir James Mackenzie Institute for Early Diagnosis, University of St Andrews. School of Chemistry, and University of St Andrews. EaSTCHEM
- Subjects
Steric effects ,Reaction mechanism ,Asymmetric ,Protonation ,Heterocycles ,010402 general chemistry ,01 natural sciences ,Catalysis ,Enamine ,Stereocenter ,chemistry.chemical_compound ,Nucleophile ,Computational chemistry ,fluorine ,Non-covalent interactions ,QD ,Conformational isomerism ,Asymmetric Synthesis ,Brønsted acid ,chemistry.chemical_classification ,heterocycles ,Full Paper ,010405 organic chemistry ,Organic Chemistry ,Enantioselective synthesis ,DAS ,Fluorine ,General Chemistry ,Full Papers ,QD Chemistry ,Combinatorial chemistry ,0104 chemical sciences ,chemistry ,Brønsted acids ,Brønsted–Lowry acid–base theory - Abstract
A catalytic enantioselective synthesis of heterocyclic vicinal fluoroamines is reported. A chiral Brønsted acid promotes aza‐Michael addition to fluoroalkenyl heterocycles to give a prochiral enamine intermediate that undergoes asymmetric protonation upon rearomatization. The reaction accommodates a range of azaheterocycles and nucleophiles, generating the C−F stereocentre in high enantioselectivity, and is also amenable to stereogenic C−CF3 bonds. Extensive DFT calculations provided evidence for stereocontrolled proton transfer from catalyst to substrate as the rate‐determining step, and showed the importance of steric interactions from the catalyst's alkyl groups in enforcing the high enantioselectivity. Crystal structure data show the dominance of noncovalent interactions in the core structure conformation, enabling modulation of the conformational landscape. Ramachandran‐type analysis of conformer distribution and Protein Data Bank mining indicated that benzylic fluorination by this approach has the potential to improve the potency of several marketed drugs., Chiral Brønsted acid catalysis enables the synthesis of heterocyclic vicinal fluoroamines by asymmetric protonation. The reaction accommodates a range of azaheterocycles and nucleophiles, generating the C−F stereocentre in high enantioselectivity, and allows the formation of chiral C−CF3 bonds. DFT calculations provided insight into the reaction mechanism, and conformational control of the products is elucidated.
- Published
- 2020
Catalog
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