ABSTRACT
A new synthetic method to access α-nitroso pyrroles is presented. This method utilises the nitrosonium salt NOBF4, enabling short reaction times (<10 minutes) and avoiding the harsh acidic conditions usually associated with pyrrole nitrosation. Application of this procedure to diarylated pyrroles yielded several novel nitroso-pyrroles. Modifications to the method, through exclusion of air and inclusion of a mild base, allowed for the nitrosation of pyrroles bearing aryl groups substituted with electron-donating groups. Attempts to nitrosylate pyrroles bearing alkyl substituents resulted in the formation of a dimeric material composed of a pyrrolic unit and a 2-hydroxyimino-protected 1,5-dihydro-2H-pyrrol-2-one.
ABSTRACT
This article describes the synthesis and photophysical properties of a series of BODIPY photosensitisers that feature tellurophene motifs appended at the boron centre. These compounds were obtained via nucleophilic substitution of various F-BODIPYs with lithiated tellurophene. The synthetic scope, photophysical characteristics and photosensitisation properties are discussed. Structural modifications around the BODIPY core resulted in an eight-fold improvement in light IC50 values compared to previous designs.
ABSTRACT
Reported herein are the synthesis and characterization of BODIPYs bearing heterocycles at boron. To synthesize this series, various chalcogenophenes (furan, thiophene, selenophene, and tellurophene) were lithiated and then used as nucleophiles to attack the boron center of a parent F-BODIPY. Compounds in the series were compared with respect to their photophysical and structural properties, and trends were discussed. By virtue of the "heavy atom effect", as the mass of the heterocycle appended to the BODIPY core increases, compounds exhibit a higher singlet oxygen quantum yield. The BODIPY with tellurophene at boron exhibits the highest quantum yield (ΦΔ = 0.68) in the series and reduced emission (Φf = 0.01).
ABSTRACT
Active radiometric reflectance is useful to determine plant characteristics in field conditions. However, the physics of silicone diode-based sensing are temperature sensitive, where a change in temperature affects photoconductive resistance. High-throughput plant phenotyping (HTPP) is a modern approach using sensors often mounted to proximal based platforms for spatiotemporal measurements of field grown plants. Yet HTPP systems and their sensors are subject to the temperature extremes where plants are grown, and this may affect overall performance and accuracy. The purpose of this study was to characterize the only customizable proximal active reflectance sensor available for HTPP research, including a 10 °C increase in temperature during sensor warmup and in field conditions, and to suggest an operational use approach for researchers. Sensor performance was measured at 1.2 m using large titanium-dioxide white painted field normalization reference panels and the expected detector unity values as well as sensor body temperatures were recorded. The white panel reference measurements illustrated that individual filtered sensor detectors subjected to the same thermal change can behave differently. Across 361 observations of all filtered detectors before and after field collections where temperature changed by more than one degree, values changed an average of 0.24% per 1 °C. Recommendations based on years of sensor control data and plant field phenotyping agricultural research are provided to support ACS-470 researchers by using white panel normalization and sensor temperature stabilization.
Subject(s)
Plants , TemperatureABSTRACT
Background: The first wave of the SARS-CoV-2 global pandemic in early 2020 required a rapid roll-out of infection prevention and control (IPC) training for healthcare workers (HCW), including use of appropriate personal protective equipment (PPE). Education about respiratory droplet and aerosol transmission was of paramount importance to ensure safe working practices and improve confidence. Methods: A joint working group of Infectious Diseases and IPC staff developed a 'train the trainers' programme, to be rapidly deployed over a three-week period. This model utilised a snowballing approach, training selected staff with the intention that they would train their teams, facilitating swift cascading of information. Targeted invitations prompted staff from diverse departments of the hospital to attend. Pre- and post-session questionnaires evaluated staff confidence with regard to appropriate PPE use. Results: The programme trained 130 HCW over a three week period, was well received and led to increased confidence with PPE use amongst staff. Real-time evaluation ensured content could be adapted to the specific needs of HCW involved. We highlight perceived gaps in training despite existing and enhanced training structures. Conclusion: Provision of face-to-face training in transmission-based precautions, including PPE use, is required to maintain confidence in safe and appropriate IPC amongst hospital staff. We highlight the importance of including non-clinical staff in PPE educational programmes, recognising that these roles are vital for patient care and are frequently patient-facing. We recommend adopting the train the trainers model to facilitate rapid dissemination of education, with interactive multidisciplinary training in future outbreaks to improve HCW confidence and effective IPC.
ABSTRACT
This organizational case study addresses the research question: What are the experiences of staff who work in a novel in-reach rehabilitation and recovery service for people with profound and enduring mental health needs? Fifteen purposefully sampled staff were recruited from across a novel mental health service that embeds the community sector within inpatient provision. The sample comprises twelve National Health Service and three community voluntary organization staff (four men and eleven women). Data were generated via photo-elicitation in which interviews focused on the photographs participants brought to help convey their experiences of the Service. Interpretative phenomenological analysis was used to analyse the transcripts. The analysis demonstrates that participants are oriented towards five 'meta-questions': What is recovery? Who is valued and how is it demonstrated? Why are you frustrated in doing the best job you can and what support do you need? How can change occur in staff practices and approaches in an environment embedded in history? and How do we make the Service work in the context of constraints? Eight paired themes were also identified regarding staff experience of the Service: hope and individuality; culture and power; communication and confidence; accountability and limitations. The conclusions of this organizational case study have wide relevance to clinical practice: staff (i) place importance on promoting and developing greater awareness of different approaches to care; (ii) aspire to develop better communication across multidisciplinary teams and (iii) desire greater awareness of the complexities of risk to improve staff confidence.
Subject(s)
Mental Health Services , Mental Health , Male , Humans , Female , State Medicine , Inpatients/psychology , Qualitative ResearchABSTRACT
PURPOSE OF REVIEW: Within the context of palliative care, existential suffering (ES) can be an exclusive source of suffering or intertwined with physical pain and/or psychological and spiritual suffering. With newly emerging modalities for addressing this phenomenon and its increasing salience given that many patients cite ES as a significant contributing factor to requests for hastened death, a review of recent interventions for addressing ES at the end of life is timely. RECENT FINDINGS: This review of newer approaches to dealing with ES in the palliative context suggests some promising new modalities and pharmacological interventions, such as brain stimulation and the use of psychedelics. The use of other pharmacological interventions, such as palliative sedation and lethal injections, solely for the alleviation of existential distress remains ethically controversial and difficult to disentangle from other forms of suffering, not least because a clear clinical definition of ES has yet to emerge in the literature. SUMMARY: The evaluation of end-of-life (EOL) ES mitigating tools should also consider how broader contexts, such as institutional arrangements and barriers, and cultural factors may influence the optimal management of dying persons' ES in the palliative care setting.
Subject(s)
Terminal Care , Humans , Terminal Care/psychology , Stress, Psychological/psychology , Palliative Care/psychology , Pain , DeathABSTRACT
OBJECTIVES: Project ADAM (Automated Defibrillators in Adam's Memory) is a national collaborative to improve outcomes for out-of-hospital sudden cardiac arrest. Given Project ADAM's expansion, we sought to identify effective methods to partner with community leaders and understand barriers to engagement. Our aim was to establish effective practices to guide affiliates and optimize site operations and partnerships. METHODS: We conducted a survey of all Project ADAM sites in 2020. Medical Directors and Program Coordinators were included for generalizability. The survey consisted of 20 questions covering the domains of communication, goals for partner organizations, partnership barriers, staff time commitments, and Project ADAM program needs. RESULTS: Thirty-one members responded: 14 Medical Directors and 17 Program Coordinators. E-mail was the predominant method to initiate (58%) and maintain (87%) contact with partner organizations, though telephone (21%) and in-person visits (14%) were common for initiating contact. Presentations at school board, Emergency Medical Services, and athletic director meetings and student/family testimonials were powerful engagement tools. Barriers to partnership varied, revolving around limited school budgets, overburdened staff, and Covid-19. Limited time, difficulty coordinating schedules, and lack of dedicated resources were common challenges for Project ADAM sites. Only 36% of Medical Directors receive institutional recognition of Project ADAM effort. CONCLUSIONS: Project ADAM's partnership with community stakeholders creates unique opportunities and challenges. Optimal communication methods should be identified early for each school, with regular interaction for long-term success. Institutional recognition of Project ADAM efforts may boost success. Additionally, the Covid-19 pandemic created numerous challenges and may spur operational changes.
Subject(s)
COVID-19 , Emergency Medical Services , Humans , Pandemics , Death, Sudden, Cardiac/prevention & control , SchoolsABSTRACT
BACKGROUND: Dysphagia post head and neck cancer (HNC) multimodality treatment is attributed to reduced pharyngeal strength. We hypothesized that pharyngeal tongue base augmentation for dysphagia (PAD therapy) would increase pharyngeal pressures during swallowing thereby improving swallow symptoms. METHODS: Adults with moderate-severe dysphagia post-HNC treatment had PAD therapy using a temporary filler (hyaluronic acid [HA]), with follow-up long-lasting lipofilling. Swallowing preprocedure and postprocedure was assessed with the Sydney Swallow Questionnaire (SSQ), High-Resolution Pharyngeal Manometry (HRPM), and Videofluoroscopic Swallowing Study (VFSS). Statistical comparison utilized paired tests. RESULTS: Six participants (all male; median age 64 years [IQR 56, 71]) underwent PAD therapy at a median of 47 [IQR 8, 95] months post-treatment. SSQ scores reduced from baseline (mean 1069 [95%CI 703, 1434]) to post-HA (mean 579 [76, 1081], p > 0.05), and post-lipofilling (491 [95%CI 913, 789], p = 0.003, n = 4). Individual participants demonstrated reduced Swallow Risk Index, Bolus Presence Time, and increased Upper Esophageal Sphincter opening, but mesopharyngeal contractile pressures were unchanged. VFSS measures of aspiration, residue, and severity were unchanged. CONCLUSIONS: Novel PAD therapy is safe and improves dysphagia symptoms. Biomechanical swallowing changes are suggestive of more efficacious bolus propulsion with conservative filler volume, but this was unable to resolve residue or aspiration measures.
Subject(s)
Deglutition Disorders , Head and Neck Neoplasms , Adult , Deglutition , Deglutition Disorders/diagnosis , Deglutition Disorders/etiology , Deglutition Disorders/therapy , Esophageal Sphincter, Upper , Head and Neck Neoplasms/complications , Humans , Male , Middle Aged , Pharynx , TongueABSTRACT
Recent synthetic achievements have led to 4,4-disubstituted-4-bora-3a,4a-diaza-s-indacenes (BODIPYs) with varying substituents at the meso, pyrrolic and/or boron sites, with each influencing photophysical properties and utility. This Feature article gives an overview of chemistry at the boron atom in BODIPYs, highlighting our contributions that evolved from synthetic curiosities and now offer this dipyrrolic skeleton potential across a wider range of applications. We first summarise preparative routes to BODIPYs through complexation of boron with the dipyrrinato ligand. The role of boron in protecting dipyrrins is then discussed, followed by strategies by which to achieve facile substitution at the boron atom.
Subject(s)
Boron , Fluorescent Dyes , Boron/chemistry , Boron Compounds/chemistry , Fluorescent Dyes/chemistry , Pyrroles/chemistryABSTRACT
Bemisia tabaci (MEAM1) represents a species of economic importance in soybean. One of the obstacles to the management of B. tabaci is the quantification of damage by the pest because damage is indirectly inferred through losses in productivity. The objective of this study was to characterize the influence of B. tabaci feeding on soybean by assessing effects on photosynthetic parameters and the sugar and starch content of soybean leaves. The goal was to identify the optimal parameter to directly quantify pest damage on crop yield. Correlation networks were created among data on sugar content (fructose, glucose, and sucrose), starch and photosynthetic parameters (initial fluorescence, performance index on absorption basis, and turn-over number), and the number of nymphs at each of three infestations level (low, medium, and high) during both the vegetative and reproductive stage of the crop. In general, nymphs were more abundant during the vegetative stage. Starch content was strongly correlated with nymph density. A strong positive correlation was observed between fructose and nymph density during the vegetative stage. Among the photosynthetic parameters, the turn-over number N was positively correlated with nymph density at a low-infestation level and negatively correlated with nymphs when they occurred at a high-infestation level. B. tabaci feeding affected the plant's physiology and its interaction is reflected in part by the relationships among photosynthetic parameters as well as the levels of sugars and starch. This understanding might be useful in developing better monitoring tools for pest management.
ABSTRACT
PURPOSE: To explore the attitudes, beliefs and experiences pertaining to the management of prescribed and unprescribed medications among community-dwelling adults with spinal cord injury/dysfunction (SCI/D) in Ontario, Canada. MATERIALS AND METHODS: In-depth semi-structured interviews were conducted by telephone. Each interview was audio-recorded, transcribed verbatim and analyzed using inductive thematic analysis. RESULTS: Of the 19 participants, 11 were male and 8 were female, with an age range from 36 to 76 years; 14 participants had traumatic SCI and 5 had non-traumatic spinal cord dysfunction. All but three participants were taking five or more medications, including prescription medications, over-the-counter medications and natural health products. The three main themes identified were: disruptive nature of medications, fear of negative outcomes and self-management: playing a critical role. CONCLUSIONS: Medication management is a complex, multifaceted and non-linear process. Persons with SCI/D described experiences with medication-taking that are not well understood by current medication management frameworks. Thus, it is essential to broaden our lens and situate persons with SCI/D medication-taking experiences within self-management frameworks to allow for a more comprehensive and reflective understanding of their experiences. Based on the findings from this study, recommendations for future research, practice and policy have been suggested.IMPLICATIONS FOR REHABILITATIONPersons with spinal cord injury/dysfunction identified numerous challenges and concerns with medication use post-injury.Educational medication management programs should be implemented post-discharge to improve the state of knowledge around medications (indication, side effects, strategies for taking medications) and how to optimize medication management.In order to optimize experiences and outcomes, there is a need for explicit and ongoing discussions around medication management between persons with spinal cord injury/dysfunction and their healthcare providers.
Subject(s)
Independent Living , Spinal Cord Injuries , Adult , Aftercare , Aged , Female , Humans , Male , Middle Aged , Ontario , Patient Discharge , Qualitative Research , Spinal Cord Injuries/drug therapyABSTRACT
BACKGROUND: People who take medications often experience challenges including making decisions about risks versus benefits and integrating medication management with all aspects of life (e.g., social and work responsibilities). Existing medication self-management frameworks are primarily adherence-focused and lack integrating holistic perspectives. OBJECTIVE: To explore the priorities of people with chronic medication experience (i.e., take at least 1 medication daily for at least 3 months) and what they can contribute to the understanding of medication self-management. METHODS: Concept mapping is a participatory, mixed-methods approach with 3 stages: brainstorming, sorting/rating, and mapping. Group brainstorming discussions were held with participants who generated statements about what mattered to them regarding medications in their everyday lives. In sorting/rating, individual participants grouped statements into thematic piles and rated their importance and feasibility. During mapping, a subset of participants discussed and agreed on a visual map and named the statement clusters. Following mapping, the researchers analyzed rating results, stratified by participant characteristics (gender, age, duration of medication use, number of medications, and chronic conditions). RESULTS: Sixty-three participants generated 1044 statements during 8 brainstorming sessions, which the researchers synthesized into 94 statements. Fifty-four participants individually sorted and rated the statements. Most statements were rated highly on both importance and feasibility, regardless of participant characteristics. Eight participants attended the mapping session. The final map had 9 thematic clusters, which were named by participants as: 1) researching and becoming educated about medications; 2) social support; 3) effectiveness of medication; 4) self-ownership of medication; 5) ease of use; 6) convenience and accessibility; 7) information provided by healthcare provider; 8) personal interactions with healthcare provider; and 9) patient involvement and trust. CONCLUSIONS: Results enhance existing medication management frameworks by providing a more comprehensive perspective. Understanding medication self-management requires more research that incorporates and prioritizes the perspectives of individuals who manage their medications.
Subject(s)
Independent Living , Self-Management , Adult , Health Personnel , Humans , Patient Participation , Social SupportABSTRACT
The synthesis and characterization of the first BODIPY appended to the five-membered heterocylic tellurophene [Te] moiety is reported. By incorporating tellurophene at the meso position, the tellurophene-appended boron-dipyrromethene dye (BODIPY) acts as a multimodal agent, becoming a potent photosensitizer with a mass cytometry tag. To synthesize the compound, we developed a method to enable late-stage Suzuki-Miyaura coupling by preparing and isolating tellurophene-2-BPin in a one-step procedure from the parent tellurophene. Coupling to a meso-substituted BODIPY functionalized with a pendant aryl bromide provides the desired tellurophene-appended BODIPY. This compound demonstrated a singlet oxygen quantum yield of 0.26 ± 0.01 and produced a light dose-dependent cytotoxicity with nanomolar IC50 values against 2D cultured HeLa cells and high efficacy against 3D cultured HeLa tumor spheroids, proving to be a strong photosensitizer. The presence of the tellurophene moiety could be detected using mass cytometry, thus showcasing the ability of a tellurophene-appended BODIPY as a novel photodynamic-therapy-mass-cytometry theranostic agent.
ABSTRACT
The study of phenotypes that reveal mechanisms of adaptation to drought and heat stress is crucial for the development of climate resilient crops in the face of climate uncertainty. The leaf metabolome effectively summarizes stress-driven perturbations of the plant physiological status and represents an intermediate phenotype that bridges the plant genome and phenome. The objective of this study was to analyze the effect of water deficit and heat stress on the leaf metabolome of 22 genetically diverse accessions of upland cotton grown in the Arizona low desert over two consecutive years. Results revealed that membrane lipid remodeling was the main leaf mechanism of adaptation to drought. The magnitude of metabolic adaptations to drought, which had an impact on fiber traits, was found to be quantitatively and qualitatively associated with different stress severity levels during the two years of the field trial. Leaf-level hyperspectral reflectance data were also used to predict the leaf metabolite profiles of the cotton accessions. Multivariate statistical models using hyperspectral data accurately estimated (R 2 > 0.7 in â¼34% of the metabolites) and predicted (Q 2 > 0.5 in 15-25% of the metabolites) many leaf metabolites. Predicted values of metabolites could efficiently discriminate stressed and non-stressed samples and reveal which regions of the reflectance spectrum were the most informative for predictions. Combined together, these findings suggest that hyperspectral sensors can be used for the rapid, non-destructive estimation of leaf metabolites, which can summarize the plant physiological status.
ABSTRACT
Rationale: Two distinct subphenotypes have been identified in acute respiratory distress syndrome (ARDS), but the presence of subgroups in ARDS associated with coronavirus disease (COVID-19) is unknown. Objectives: To identify clinically relevant, novel subgroups in COVID-19-related ARDS and compare them with previously described ARDS subphenotypes. Methods: Eligible participants were adults with COVID-19 and ARDS at Columbia University Irving Medical Center. Latent class analysis was used to identify subgroups with baseline clinical, respiratory, and laboratory data serving as partitioning variables. A previously developed machine learning model was used to classify patients as the hypoinflammatory and hyperinflammatory subphenotypes. Baseline characteristics and clinical outcomes were compared between subgroups. Heterogeneity of treatment effect for corticosteroid use in subgroups was tested. Measurements and Main Results: From March 2, 2020, to April 30, 2020, 483 patients with COVID-19-related ARDS met study criteria. A two-class latent class analysis model best fit the population (P = 0.0075). Class 2 (23%) had higher proinflammatory markers, troponin, creatinine, and lactate, lower bicarbonate, and lower blood pressure than class 1 (77%). Ninety-day mortality was higher in class 2 versus class 1 (75% vs. 48%; P < 0.0001). Considerable overlap was observed between these subgroups and ARDS subphenotypes. Severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) RT-PCR cycle threshold was associated with mortality in the hypoinflammatory but not the hyperinflammatory phenotype. Heterogeneity of treatment effect to corticosteroids was observed (P = 0.0295), with improved mortality in the hyperinflammatory phenotype and worse mortality in the hypoinflammatory phenotype, with the caveat that corticosteroid treatment was not randomized. Conclusions: We identified two COVID-19-related ARDS subgroups with differential outcomes, similar to previously described ARDS subphenotypes. SARS-CoV-2 PCR cycle threshold had differential value for predicting mortality in the subphenotypes. The subphenotypes had differential treatment responses to corticosteroids.
Subject(s)
Adrenal Cortex Hormones/therapeutic use , COVID-19 Drug Treatment , Latent Class Analysis , Respiratory Distress Syndrome/drug therapy , Aged , COVID-19/complications , Cohort Studies , Female , Humans , Male , Middle Aged , Respiratory Distress Syndrome/classification , Respiratory Distress Syndrome/etiology , Retrospective StudiesABSTRACT
Minerals preserve the oldest, most persistent soil carbon, and mineral characteristics appear to play a critical role in the formation of soil organic matter (SOM) associations. To test the hypothesis that roots, and differences in carbon source and microbial communities, influence mineral SOM associations over short timescales, we incubated permeable mineral bags in soil microcosms with and without plants, inside a 13CO2 labeling chamber. Mineral bags contained quartz, ferrihydrite, kaolinite, or soil minerals isolated via density separation. Using 13C-nuclear magnetic resonance, Fourier transform ion cyclotron resonance mass spectrometry, and lipidomics, we traced carbon deposition onto minerals, characterizing total carbon, 13C enrichment, and SOM chemistry over three growth stages of Avena barbata. Carbon accumulation was rapid and mineral-dependent but slowed with time; the accumulated amount was not significantly affected by root presence. However, plant roots strongly shaped the chemistry of mineral-associated SOM. Minerals incubated in a plant rhizosphere were associated with a more diverse array of compounds (with different functional groups-carbonyl, aromatics, carbohydrates, and lipids) than minerals incubated in an unplanted bulk soil control. We also found that many of the lipids that sorbed to minerals were microbially derived, including many fungal lipids. Together, our data suggest that diverse rhizosphere-derived compounds may represent a transient fraction of mineral SOM, rapidly exchanging with mineral surfaces.
Subject(s)
Carbon , Soil , Minerals , Rhizosphere , Soil MicrobiologyABSTRACT
INTRODUCTION: Transplantation is the optimal management for patients with end-stage renal disease. In Ethiopia, the first national kidney transplantation center was opened at St. Paul's Hospital Millennium Medical College in September 2015. The aim of this study was to explore providers' views and experiences of the past to present at this center. METHODS: A qualitative study design was employed from 1st November to 15th December, 2019. To ensure that appropriate informants would provide rich study data, 8 health care providers and top management members were purposefully chosen for in-depth interviews. A maximum variation sampling method was considered to include a representative sample of informants. Interviews were digitally audio-recorded, and transcribed verbatim. Transcribed data was coded and analyzed using Qualitative Data Analysis (QDA) Minor Lite software and Microsoft-Excel. RESULT: The participants (5 males and 3 females) approached were from different departments of the renal transplant center, and the main hospital. Eight main themes and 18 sub-themes were generated initially from all interviews totaling to 109 index codes. Further evaluation and recoding retained 5 main themes, and 14 sub-themes. The main themes are; challenges experienced during and after launching the center, commitment, sympathy and satisfaction, outcomes of renal transplant, actions to improve the quality of service, and how the transplant center should operate. Providers claim that they discharge their responsibilities through proper commitment and compassion, paying no attention to incentive packages. They also explained that renal transplantation would have all the outcomes related to economic, humanistic and clinical facets. CONCLUSION AND RECOMMENDATION: A multitude of challenges were faced during and after the establishment of the first renal transplant center in Ethiopia. Providers discharge their responsibility through a proper compassion for patients. Concerned stakeholders should actively collaborate to improve the quality of renal transplant services in the center.
ABSTRACT
Asthma therapy, including monoclonal antibodies, was not associated with #COVID19 infection or hospitalisation in a UK severe asthma population. Shielding led to a reported worsening of mental health in nearly half of patients contacted (47%). https://bit.ly/3jImUsG.