Fast, Efficient, Catalyst-Free Epoxidation of Butyl Rubber Using Oxone/Acetone for Improved Filler Dispersion.

Incorporation of a polar filler such as silica into a nonpolar rubber matrix is challenging and energy consuming due to their large difference in polarity. Epoxidation of carbon-carbon double bonds in unsaturated rubber, especially for rubber with low unsaturation such as butyl rubber, is an effective method to introduce polar functional groups to the rubber macromolecules for better filler dispersion. Although different epoxidation reagents including hydrogen peroxide (H2O2), peracid, and meta-chloroperoxybenzoic acid (mCPBA) have been previously reported, these reagents have different drawbacks. In this article, a metal-free epoxidation reagent, dimethyl dioxirane (DMDO), generated from acetone and Oxone is explored for efficient epoxidation of rubber with low unsaturation. The effects of the addition manner of the reactant Oxone and buffer sodium bicarbonate (NaHCO3) and reaction temperature on the epoxide formation are studied. Compared to peracid, a faster and more efficient epoxidation without the generation of a ring-opened product is achieved when DMDO is used as the epoxidation reagent. Furthermore, it is found that the epoxidation using DMDO is not sensitive to the water concentration in the rubber solution up to 20 wt %. The addition of quaternary ammonium salt as a phase transfer catalyst not only improves the conversion but also further increases the water tolerance to 25 wt %. The reaction conditions for preparation of epoxidized butyl rubber with different percentages of epoxide group are optimized by Design of Experiments (DoE). At the end, improved dispersion of silica in the matrix of epoxidized butyl rubber is achieved, as revealed by the rubber process analyzer (RPA) and atomic force microscopy (AFM).

Pain experiences of marginalized children in the emergency department: A scoping review protocol.

INTRODUCTION: Pain affects all children, and in hospitals across North America, this pain is often undertreated. Children who visit the emergency department (ED) experience similar undertreatment, and they will often experience a painful procedure as part of their diagnostic journey. Further, children and their caregivers who experience social injustices through marginalization are more likely to experience healthcare disparities in their pain management. Still, most of our knowledge about children's pain management comes from research focused on well-educated, white children and caregivers from a middle- or upper-class background. The aim of this scoping review is to identify, map, and describe existing research on (a) how aspects of marginalization are documented in randomized controlled trials related to children's pain and (b) to understand the pain treatment and experiences of marginalized children and their caregivers in the ED setting. METHODS AND ANALYSIS: The review will follow Joanna Briggs Institute methodology for scoping reviews using the Participant, Concept, Context (PCC) framework and key terms related to children, youth, pain, ED, and aspects of marginalization. We will search Medline, Embase, PsychInfo, CINAHL, Web of Science, Cochrane Library Trials, iPortal, and Native Health Database for articles published in the last 10 years to identify records that meet our inclusion criteria. We will screen articles in a two-step process using two reviewers during the abstract and full-text screening stages. Data will be extracted using Covidence for data management and we will use a narrative approach to synthesize the data. ETHICS AND DISSEMINATION: Ethical approval is not required for this review. Findings will be disseminated in academic manuscripts, at academic conferences, and with partners and knowledge users including funders of pain research and healthcare professionals. Results of this scoping review will inform subsequent quantitative and qualitative studies regarding pain experiences and treatment of marginalized children in the ED.

Radical Stereochemistry: Accounting for Diastereomers in Kinetic Mechanism Development.

Recent work in combustion and atmospheric chemistry has revealed cases in which diastereomers must be distinguished to accurately model a reacting flow. This paper presents an open-source framework for introducing such stereoisomer resolution into a kinetic mechanism. We detail our definitions and algorithms for labeling and enumerating the stereoisomers of a molecule and then generalize our system to describe the transition state (TS) of a reaction. This allows for the stereospecific enumeration of reactants and products while accounting for "fleeting" stereochemistry that is unique to the TS. We also present the AutoMech Chemical Identifier (AMChI), an InChI-like string identifier that accounts for stereocenters omitted by InChI. This identifier is extended to describe the TSs of reactions, providing a universal lookup key for specific reaction channels. The final piece of our methodology is an analytic formula to remove redundancy from a stereoresolved mechanism when its enantiomers exist as a racemic mixture, making it as compact as possible while fully accounting for the differences between diastereomers. In applying our methodology to two subsets of the NUIGMech1.1 mechanism, we find that our approach reduces the extra species added for large-fuel oxidation from 2231 (133%, full expansion) to 694 (41%, nonredundant expansion). We also find that for pyrolysis more than a quarter of the species in the expanded mechanism cannot be properly described by an InChI string, requiring an AMChI string to communicate their identity. Finally, we find that roughly one-quarter of the large-fuel oxidation reactions and one-third of the pyrolysis reactions include fleeting TS stereochemistry, which may have relevant effects on their kinetics.

Parents' User Experience Accessing and Using a Web-Based Map of COVID-19 Recommendations for Health Decision-Making: Qualitative Descriptive Study.

BACKGROUND: The eCOVID19 Recommendations Map & Gateway to Contextualization (RecMap) website was developed to identify all COVID-19 guidelines, assess the credibility and trustworthiness of the guidelines, and make recommendations understandable to various stakeholder groups. To date, little has been done to understand and explore parents' experiences when accessing and using the RecMap website for COVID-19 health decision-making. OBJECTIVE: To explore (1) where parents look for COVID-19 health information and why, (2) parents' user experience when accessing and using the RecMap website to make health decisions, and (3) what knowledge mobilization activities are needed to increase parents' awareness, use, and engagement with the RecMap website. METHODS: We conducted a qualitative descriptive study using semistructured interviews and a think-aloud activity with parents of children aged 18 years or younger living in Canada. Participants were asked to provide feedback on the RecMap website and to "think aloud" as they navigated the website to find relevant COVID-19 health recommendations. Demographic information was collected using a web-based questionnaire. A hybrid deductive and inductive thematic approach guided analysis and data synthesis. RESULTS: A total of 21 participants (13/21, 62% mothers) were interviewed and participated in a think-aloud activity. The data were categorized into four sections, representative of key elements that deductively and inductively emerged from the data: (1) parent information seeking behaviors and preferences for COVID-19, (2) RecMap website usability, (3) perceived usefulness of the RecMap website, and (4) knowledge mobilization strategies to increase awareness, use, and engagement of the RecMap website. Parents primarily used the internet to find COVID-19 information and focused on sources that they determined to be credible, trustworthy, simple, and engaging. As the pandemic evolved, participants' information-seeking behaviors changed, specifically their topics of interest and search frequency. Most parents were not aware of the RecMap website before this study but found satisfaction with its concept and layout and expressed intentions to use and share it with others. Parents experienced some barriers to using the RecMap website and suggested key areas for improvement to facilitate its usability and perceived usefulness. Recommendations included a more user-friendly home page for lay audiences (separate public-facing user interface), improving the search and filter options, quicker navigation, clearer titles, more family-friendly graphics, and improving mobile-friendly access. Several strategies to disseminate the RecMap website were also expressed, including a mix of traditional and nontraditional methods (handouts and social media) in credible and high-traffic locations that parents frequent often. CONCLUSIONS: Overall, parents liked the concept of the RecMap website but had some suggestions to improve its usability (language, navigation, and website interface). These findings can be used to improve the RecMap website for parents and offer insight for the development and dissemination of effective web-based health information tools and resources for the general public.

Reduced Freshwater Mussel Juvenile Production as a Result of Agricultural and Urban Contaminant Mixture Exposures.

Freshwater mussels provide invaluable ecological services but are threatened by habitat alteration, poor water quality, invasive species, climate change, and contaminants, including contaminants of emerging concern (CECs). Contaminants of emerging concerns are well documented in aquatic environments, including the Great Lakes Basin, but limited information is available on how environmentally relevant mixtures affect freshwater mussel biology throughout their varied life stages. Our main goal was to assess mussels' reproductive output in response to exposure to agricultural and urban CEC mixtures during glochidial development through juvenile transformation and excystment focusing on how exposure duration and treatment affect: (1) the number of glochidia prematurely released by brooding females, (2) glochidial transformation through host-fish excystment, and (3) the number of fully metamorphosed juveniles able to continue the lifecycle. Mussels and host fish were exposed to either a control water (CW), control ethanol (CE), agriculture CEC mixture (AM), or urban CEC mixture (UM) for 40 and 100 days. We found no effect from treatment or exposure duration on the number of glochidia prematurely released. Fewer partially and fully metamorphosed AM juveniles were observed during the 100-day exposure, compared with the 40-day. During the 40-day exposure, CW produced more fully metamorphosed individuals compared with CE and UM, but during the 100-day exposure AM produced more fully metamorphosed individuals compared with the CW. There was reduction in fully metamorphosed juveniles compared with partially metamorphosed for CE and UM during the 40-day exposure, as well as in the CW during the 100-day exposure. These results will be important for understanding how mussel populations are affected by CEC exposure. The experiments also yielded many insights for laboratory toxicology exposure studies. Environ Toxicol Chem 2024;43:1112-1125. © 2024 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC. This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.

Consequences of the Coronavirus disease 2019 pandemic on child and adolescent mental, psychosocial, and physical health: A scoping review and interactive evidence map.

Effects of the Coronavirus disease 2019 (COVID-19) pandemic on children stem beyond immediate infectious and post-infectious risks. Our aim was to conduct a scoping review and produce an online Interactive Evidence Map (IEM) highlighting available literature around unintended effects of the pandemic on children's and adolescents' mental, psychosocial, and physical health. A search was run monthly in MEDLINE, PsycINFO, CENTRAL, and Cochrane COVID-19 Study Register from May 1st 2021 through April 30th 2022. All articles involving children and adolescents under 18 years of age relating to any unintended mental, psychosocial, and physical health consequences of the pandemic and resultant restrictions were included. Data were extracted and topics categorized, with corresponding data uploaded into EPPI-Reviewer and transferred to EPPI-Mapper for visualization. A total of 14,555 citations were screened and 826 (6%) articles included. Most articles reported on mental health outcomes, particularly anxiety (n = 309, 37%) and depression (n = 294, 36%). Psychosocial outcomes related to lockdowns such as loneliness (n = 120, 15%) and impact on adolescent relationships with others (n = 149, 18%) were also reported. Fewer articles examined physical consequences, but those that did mostly focused on child abuse (n = 73, 9%). Overall, currently mapped literature focuses on consequences related to mental health outcomes such as anxiety and depression.

Emin: A First-Principles Thermochemical Descriptor for Predicting Molecular Synthesizability.

Predicting the synthesizability of a new molecule remains an unsolved challenge that chemists have long tackled with heuristic approaches. Here, we report a new method for predicting synthesizability using a simple yet accurate thermochemical descriptor. We introduce Emin, the energy difference between a molecule and its lowest energy constitutional isomer, as a synthesizability predictor that is accurate, physically meaningful, and first-principles based. We apply Emin to 134,000 molecules in the QM9 data set and find that Emin is accurate when used alone and reduces incorrect predictions of "synthesizable" by up to 52% when used to augment commonly used prediction methods. Our work illustrates how first-principles thermochemistry and heuristic approximations for molecular stability are complementary, opening a new direction for synthesizability prediction methods.

'It's quite a balancing act': A qualitative study of parents' experiences and information needs related to the COVID-19 pandemic.

INTRODUCTION: Throughout the coronavirus disease 2019 (COVID-19) pandemic, parents and children faced significant challenges as a result of prevention measures implemented to control the spread of the disease. Ensuring that families have access to essential health information is critical for improving health outcomes and adherence to public health recommendations. Understanding parents' experiences and information needs related to the pandemic and associated health measures (e.g., vaccination, mask wearing, social distancing, etc.) will inform the development and dissemination of resources tailored to parents' needs to support informed decision making. METHODS: We conducted a qualitative descriptive study. Between September and November 2021, parents across Canada were recruited online via social media and community organisation newsletters and listservs to participate in focus groups via Zoom. Focus groups were audio-recorded and transcribed verbatim. Data were coded and analysed using thematic analysis. Participants completed a demographic questionnaire before the focus groups (via SimpleSurveys). RESULTS: Sixty-seven parents participated in 12 focus groups between October and November 2021. In relation to experiences, parents felt they were (1) constantly trying to balance everything, and (2) trying to do their best with the information they had at the time when making decisions. Regarding information needs, parents reflected on (1) how difficult it was navigating copious amounts of changing information and finding credible sources to rely on, (2) the need for resources that were easily accessible, credible and in plain language and (3) the need for resources that were tailored to their needs to support them and their children make informed decisions. CONCLUSIONS: Trying to mitigate the risk of COVID-19 infection and adhere to public health recommendations, while balancing various factors (work, online learning, and social interactions) and navigating changing information, was overwhelming for many parents. Reflecting on their needs, parents suggested tailored resources that provided concise, credible information in plain language to help them make informed decisions and navigate conflicting information. These findings reveal important knowledge gaps and highlight areas that need to be addressed to support parents during the pandemic period and beyond. PATIENT OR PUBLIC CONTRIBUTION: Members of our established Paediatric Parent Advisory Group (P-PAG) were involved as collaborators throughout the planning (grant proposal), development and execution of the study. P-PAG members gave input on the design of the questionnaire, interview guide, recruitment strategy and interpretation of findings.

Factors associated with a negative Patient Acceptable Symptom State (PASS) response with intrauterine device placement: A retrospective survey of HER Salt Lake participants.

OBJECTIVES: In an established cohort of HER Salt Lake Contraceptive Initiative participants with a prior intrauterine device (IUD) placement, we sought to (1) define the proportion of participants who reported a negative Patient Acceptable Symptom State (PASS) response, (2) explore factors associated with an unacceptable PASS response, and (3) identify pain management preferences for IUD placement. STUDY DESIGN: A retrospective survey was sent to 1440 HER Salt Lake IUD users. A PASS question queried IUD placement pain experience acceptability. We explored associations between an unacceptable PASS response and sociodemographic, reproductive and other individual characteristics using t-tests, chi-square tests, and multivariable logistic regression. RESULTS: Of those surveyed, 620 responded (43%), and 41.6% reported an unacceptable PASS response. Those with an unacceptable PASS response reported a significantly higher experienced pain level (79.2 mm vs 51.8 mm; p < 0.01) than those with an acceptable response, were more likely to have an anxiety diagnosis (47.7% vs 37.1%; p < 0.01), and have a trauma history (33.7% vs 25.1%; p = 0.02). Most patients were not offered pain control options, but 29.4% used ibuprofen and 25.3% had a support person. Regardless of PASS response, if offered, 59.0% desired numbing medication, 56.8% ibuprofen, 51% heating pad, 33.2% support person, and 31.8% anti-anxiety medication, among others. In our multivariable logistic regression model, higher pain was associated with unacceptable PASS response (OR 1.07, 95% CI 1.05-1.08; p < 0.01). CONCLUSIONS: The common finding of unacceptable pain experiences with IUD placement may cause negative perceptions of an otherwise desirable method. Incorporation of the PASS response into IUD pain management studies could expand our pain experience understanding. IMPLICATIONS: IUD placement resulted in unacceptable pain experiences for 41.6% of respondents. Screening for anxiety and trauma history could identify at-risk patients to individualize pain management strategies. Incorporation of the PASS into future IUD pain management studies could result in a more comprehensive, patient-centered measure of patient experiences.

Understanding How Youth Search for Mental Health Information Online: A Qualitative Descriptive Study.

The objective of this study was to understand how youth search for mental health information online. Youth partners were engaged at the onset of the project and provided input throughout on the design, conduct and analysis. Individual, semi-structured interviews with Canadian youth with experience searching for mental health information online were conducted. Data collection and reflexive thematic analysis proceeded concurrently. Fourteen youth were interviewed. Four main themes related to how youth search online emerged: mind-set shapes the search process; external factors shape the search process; key attributes of helpful information; and cues affecting trustworthiness of online information. Findings can inform the development of youth-friendly online mental health information that is perceived as helpful and trustworthy by youth. Ensuring youth have access to quality online mental health information, accessible to how they search for it, is critical to the mental health and development of youth.

Four year evaluation of a parent advisory group to support a research program for knowledge translation in child health.

BACKGROUND: In 2016, we developed a pediatric parent advisory group to inform our research program which creates innovative knowledge translation (KT) tools for parents on priority topics related to acute childhood illness. We implemented a mixed methods strategy to evaluate the experiences of group members. The purpose of this paper is to present the findings from parent evaluations over four years and to discuss our experiences collaborating with the group over a multi-year period. METHODS: We conducted year-end surveys and interviews of group members to understand parents' perceptions of their experiences, group management, researcher interaction, and other outcomes of advisory group participation from 2018 to 2021. We applied a mixed methods approach, collecting and analyzing both quantitative (survey) and qualitative (survey/interview) data. Survey data were analyzed by term using descriptive statistics (i.e., frequencies, percentages). Open-ended survey responses were analyzed by conventional content analysis. Interview data were analysed thematically. RESULTS: Year-end survey response rates and interview participation varied over the years. Responses to evaluation questions were generally positive and most improved over time. Results prompted changes to improve P-PAG operations, such as changes to location of meetings, communications about the group's purpose, offering sufficient context for discussion items, and providing feedback about how members' input was used. Themes identified from the qualitative data related to the importance of certain aspects of group functioning, positive views of the group's current management, and potential areas for improvement. Parents regularly expressed a desire for more diversity in the group's membership and an interest in hearing more about how the research program's activities fit into the broader healthcare system and their impacts on health outcomes. CONCLUSIONS: Our experience in establishing, managing, and evaluating a parent advisory group over many years has resulted in valuable insights regarding patient engagement in health research and sustaining an advisory group over time. We have learned that an intentional and iterative approach with regular evaluations and responsive changes has been essential for fostering meaningful engagement. Significant resources are required to maintain the group; in turn, the group has made substantial and diverse contributions to the research program and its outputs.

We developed a parent advisory group in 2016 to support our research program in knowledge translation (KT, i.e., sharing research in accessible ways to inform decision-making) for child health. The purpose of the group is to involve parents in co-developing, evaluating, and sharing KT tools (e.g., videos, infographics). The group has also worked with researchers to inform methods and provide input on research projects and products. The group has been running for seven years and has involved different types of evaluations, including parent surveys and interviews. Parents had generally positive views of their experience with the group (including the group's management, interactions with researchers, etc.) and their responses mostly improved over the years. Based on parents' feedback, we made changes to improve the group's operations, such as changing the frequency and location of meetings, regular communications about the group's purpose, offering more context and time for individual discussion items, and providing feedback to parents about how their input was used. Parents regularly expressed a desire for more diversity in the group's membership. They also expressed an interest in hearing more about how the research program fit into the broader healthcare system and impacts on health outcomes. We have learned that it takes a large amount of time, effort, and funding to run the group; however, the parent contributions have been valuable and wide-reaching. We feel that the evaluations and responsive changes to the group over time have been essential to sustain and foster meaningful engagement and achieve the group's objectives.

Associations between social determinants of health and diabetes self-care behaviors among insured adult patients.

AIMS: This study explored the association between social determinants of health (SDOH) and diabetes care behaviors among individuals with health insurance. METHODS: Data from 57,206 US residents, representing a population of over 25.58 million adults with health insurance and diagnosed diabetes, were included in this cross-sectional analysis of data from the 2017 Behavioral Risk Factor Surveillance System. Logistic regression models were constructed to evaluate the likelihood of various diabetes care behaviors given the presence of several SDOH (e.g., food insecurity, poverty, housing insecurity, rurality). RESULTS: Most respondents exercised, ate vegetables, saw a provider for diabetes-related care in the last year, and reported checking their feet and testing their blood sugar daily. Not feeling safe (odds ratio (OR) 1.77, 95 % confidence interval (CI) 1.04, 3.01) was related to never checking blood sugar. Experiencing frequent stress was associated with a lower likelihood of exercise (OR .77, 95% CI 0.60, 0.999) and lower likelihood of checking blood sugar at least once a day (OR 0.73, 95% CI 0.54, 0.99). Food insecurity was associated with lower likelihood of vegetable consumption (OR 0.63, 95 % CI 0.47, 0.85) but a higher likelihood of checking blood sugar (OR 1.80, 95 % CI 1.26, 2.57). Low-income respondents were less likely to exercise (OR 0.72, 95 % CI 0.64, 0.80) or eat vegetables (OR 0.83, 95 % CI 0.75, 0.93) but more likely to check their feet (OR 1.19, 95 % CI 1.04, 1.35) and blood sugar at least once per day (OR 1.15, 95% CI 1.01, 1.31). Those who rent their home were also more likely to check their blood sugar (OR 1.22, 95% CI 1.07, 1.37) but less likely to have eaten vegetables in the last week (OR 0.87, 95% CI 0.78, 0.97). Respondents living in rural areas were more likely to have visited a provider in the last year (OR 1.21 95% CI 1.00, 1.47). CONCLUSIONS: SDOH can adversely affect diabetes self-care behaviors, providers should assist vulnerable patients by connecting them with community resources and providing individualized care.

Strategies for obstetricians and gynecologists to advance reproductive autonomy in a post-Roe landscape.

The monumental reversal of Roe vs Wade dramatically impacted the landscape of reproductive healthcare access in the United States. The decision most significantly affects communities that historically have been and continue to be marginalized by systemic racism, classism, and ableism within the medical system. To minimize the harm of restrictive policies that have proliferated since the Supreme Court overturned Roe, it is incumbent on obstetrician-gynecologists to modify practice patterns to meet the pressing reproductive health needs of their patients and communities. Change will require cross-discipline advocacy focused on advancing equity and supporting the framework of reproductive justice. Now, more than ever, obstetrician-gynecologists have a critical responsibility to implement new approaches to service delivery and education that will expand access to evidence-based, respectful, and person-centered family planning and early pregnancy care regardless of their practice location or subspecialty.

A multimethods randomized trial found that plain language versions improved adults understanding of health recommendations.

OBJECTIVES: To make informed decisions, the general population should have access to accessible and understandable health recommendations. To compare understanding, accessibility, usability, satisfaction, intention to implement, and preference of adults provided with a digital "Plain Language Recommendation" (PLR) format vs. the original "Standard Language Version" (SLV). STUDY DESIGN AND SETTING: An allocation-concealed, blinded, controlled superiority trial and a qualitative study to understand participant preferences. An international on-line survey. 488 adults with some English proficiency. 67.8% of participants identified as female, 62.3% were from the Americas, 70.1% identified as white, 32.2% had a bachelor's degree as their highest completed education, and 42% said they were very comfortable reading health information. In collaboration with patient partners, advisors, and the Cochrane Consumer Network, we developed a plain language format of guideline recommendations (PLRs) to compare their effectiveness vs. the original standard language versions (SLVs) as published in the source guideline. We selected two recommendations about COVID-19 vaccine, similar in their content, to compare our versions, one from the World Health Organization (WHO) and one from Centers for Disease Control and Prevention (CDC). The primary outcome was understanding, measured as the proportion of correct responses to seven comprehension questions. Secondary outcomes were accessibility, usability, satisfaction, preference, and intended behavior, measured on a 1-7 scale. RESULTS: Participants randomized to the PLR group had a higher proportion of correct responses to the understanding questions for the WHO recommendation (mean difference [MD] of 19.8%, 95% confidence interval [CI] 14.7-24.9%; P < 0.001) but this difference was smaller and not statistically significant for the CDC recommendation (MD of 3.9%, 95% CI -0.7% to 8.3%; P = 0.096). However, regardless of the recommendation, participants found the PLRs more accessible, (MD of 1.2 on the seven-point scale, 95% CI 0.9-1.4%; P < 0.001) and more satisfying (MD of 1.2, 95% CI 0.9-1.4%; P < 0.001). They were also more likely to follow the recommendation if they had not already followed it (MD of 1.2, 95% CI 0.7-1.8%; P < 0.001) and share it with other people they know (MD of 1.9, 95% CI 0.5-1.2%; P < 0.001). There was no significant difference in the preference between the two formats (MD of -0.3, 95% CI -0.5% to 0.03%; P = 0.078). The qualitative interviews supported and contextualized these findings. CONCLUSION: Health information provided in a PLR format improved understanding, accessibility, usability, and satisfaction and thereby has the potential to shape public decision-making behavior.

OH Roaming during the Ozonolysis of α-Pinene: A New Route to Highly Oxygenated Molecules?

The formation of low-volatility organic compounds in the ozonolysis of α-pinene, the dominant atmospheric monoterpene, provides an important route to aerosol formation. In this work, we consider a previously unexplored set of pathways for the formation of highly oxygenated molecules in α-pinene ozonolysis. Pioneering, direct experimental observations of Lester and co-workers have demonstrated a significant production of hydroxycarbonyl products in the dissociation of Criegee intermediates. Theoretical analyses indicate that this production arises from OH roaming-induced pathways during the OO fission of the vinylhydroperoxides (VHPs), which in turn come from internal H transfers in the Criegee intermediates. Ab initio kinetics computations are used here to explore the OH roaming-induced channels that arise from the ozonolysis of α-pinene. For computational reasons, the calculations consider a surrogate for α-pinene, where two spectator methyl groups are replaced with H atoms. Multireference electronic structure calculations are used to illustrate a variety of energetically accessible OH roaming pathways for the four VHPs arising from the ozonolysis of this α-pinene surrogate. Ab initio transition-state theory-based master equation calculations indicate that for the dissociation of stabilized VHPs, these OH roaming pathways are kinetically significant with a branching that generally increases from ∼20% at room temperature up to ∼70% at lower temperatures representative of the troposphere. For one of the VHPs, this branching already exceeds 60% at room temperature. For the overall ozonolysis process, these branching ratios would be greatly reduced by a limited branching to the stabilized VHP, although there would also be some modest roaming fraction for the nonthermal VHP dissociation process. The strong exothermicities of the roaming-induced isomerizations/additions and abstractions suggest new routes to fission of the cyclobutane rings. Such ring fissions would facilitate further autoxidation reactions, thereby providing a new route for producing highly oxygenated nonvolatile precursors to aerosol formation.

A stakeholder-developed logic model to improve utilization of pharmacy-prescribed contraception in Utah.

BACKGROUND: Currently, 20 states in the USA have passed policies allowing pharmacists to prescribe short-acting hormonal contraception, including pills, patches, and vaginal rings. Yet, utilization of these services remains limited. The purpose of this study was to (a) assess barriers and facilitators of pharmacy contraceptive dispensing among contraceptive users, pharmacists, and healthcare providers in Utah and (b) adapt and propose an evidence-based contraceptive intervention in the pharmacy environment. METHODS: We conducted 6 focus groups among contraceptive users, pharmacists, and healthcare providers assessing current barriers and facilitators to pharmacy prescribing. We coded transcripts of these focus groups to the Consolidated Framework for Implementation Research, Version 2.0 (CFIR) and characterized the findings based on the Expert Recommendations for Implementing Change (ERIC) Barrier-Busting tool. Based on the CFIR findings and ERIC strategies output, we adapted an existing evidence-based intervention (a contraceptive access initiative) to the Utah pharmacy environment. We then convened a pharmacy stakeholder meeting and presented elements of an Implementation Research Logic Model and obtained feedback. We coded this feedback to the CFIR framework to finalize an Implementation Research Logic Model for a proposed implementation approach to improving contraceptive prescribing. RESULTS: Initial focus group responses clustered around specific implementation barriers including financial barriers (cost for patients, as well as lack of reimbursement for pharmacist's time); lack of awareness of the service (on the part of patients, pharmacists, and health care providers); need for updated tools for contraceptive counseling and scheduling; and need for increased pharmacists education to conduct contraceptive counseling. Proposed adaptations to the existing contraceptive access intervention included development of a technology-based patient/pharmacist screener tool and a healthcare provider/pharmacist contraceptive referral network. Stakeholders identified pharmacist reimbursement as the top priority for improving utilization. CONCLUSIONS: Elements of contraceptive access initiatives mapped well as proposed implementation strategies to improving utilization of contraceptive prescribing in pharmacies.

Expression and Activity of the NF-κB Subunits in Chronic Lymphocytic Leukaemia: A Role for RelB and Non-Canonical Signalling.

BACKGROUND: Canonical NF-κB signalling by p65 (RelA) confers chemo-resistance and poor survival in chronic lymphocytic leukaemia (CLL). The role of non-canonical NF-κB signalling (leading to RelB and p52 subunit activation) in CLL is less understood, but given its importance in other B-cell tumour types, we theorised that RelB and p52 may also contribute to the pathology of CLL. METHODS: DNA binding activity of all five NF-kB subunits, p65, p50, RelB, p52, and c-Rel, was quantified using ELISA and correlated to ex vivo chemoresistance, CD40L-stimulated signalling (to mimic the lymph node microenvironment), and clinical data. RESULTS: Importantly, we show for the first time that high basal levels of RelB DNA binding correlate with nuclear RelB protein expression and are associated with del(11q), ATM dysfunction, unmutated IGHV genes, and shorter survival. High levels of nuclear p65 are prevalent in del(17p) cases (including treatment-naïve patients) and also correlate with the outcome. CD40L-stimulation resulted in rapid RelB activation, phosphorylation and processing of p100, and subsequent CLL cell proliferation. CONCLUSIONS: These data highlight a role for RelB in driving CLL cell tumour growth in a subset of patients and therefore strategies designed to inhibit non-canonical NF-κB signalling represent a novel approach that will have therapeutic benefit in CLL.

Establishing priorities in child health: Giving parents and youth a voice.

Parents and youth across Alberta were engaged to identify specific research questions that are a priority to them. Two lists, containing 27 topics were developed with local parent and youth advisory groups, and sent to participants via online questionnaires. Topics were rated from one (least important) to five (most important) and ranked in order of priority. Initial questionnaires were completed by 263 (46%) parents and 308 (54%) youth. Parents rated five topics (behaviour, learning, and developmental disorders; mental health; food, environment and lifestyle; quality of health care; and vaccines) and youth rated four topics (brain and nerve health; mental health; quality of health care; and vaccines) as a high priority. Research questions stemming from 4 parent (12 [5%]) and 6 youth (21 [7%]) focus group discussions were then ranked in a second questionnaire, completed by 43 (43%) parents and 56 (56%) youth. Parents' highest ranked research question was 'What is the effect of screen time on cognition and neurodevelopment for children and adolescents?', while the highest ranked question from youth was 'What are the early signs of anxiety and depression and when should an individual seek help?'. These topics highlight areas that are important to parents and youth where funding, research, and knowledge mobilization efforts should be directed.

OH Roaming and Beyond in the Unimolecular Decay of the Methyl-Ethyl-Substituted Criegee Intermediate: Observations and Predictions.

Alkene ozonolysis generates short-lived Criegee intermediates that are a significant source of hydroxyl (OH) radicals. This study demonstrates that roaming of the separating OH radicals can yield alternate hydroxycarbonyl products, thereby reducing the OH yield. Specifically, hydroxybutanone has been detected as a stable product arising from roaming in the unimolecular decay of the methyl-ethyl-substituted Criegee intermediate (MECI) under thermal flow cell conditions. The dynamical features of this novel multistage dissociation plus a roaming unimolecular decay process have also been examined with ab initio kinetics calculations. Experimentally, hydroxybutanone isomers are distinguished from the isomeric MECI by their higher ionization threshold and distinctive photoionization spectra. Moreover, the exponential rise of the hydroxybutanone kinetic time profile matches that for the unimolecular decay of MECI. A weaker methyl vinyl ketone (MVK) photoionization signal is also attributed to OH roaming. Complementary multireference electronic structure calculations have been utilized to map the unimolecular decay pathways for MECI, starting with 1,4 H atom transfer from a methyl or methylene group to the terminal oxygen, followed by roaming of the separating OH and butanonyl radicals in the long-range region of the potential. Roaming via reorientation and the addition of OH to the vinyl group of butanonyl is shown to yield hydroxybutanone, and subsequent C-O elongation and H-transfer can lead to MVK. A comprehensive theoretical kinetic analysis has been conducted to evaluate rate constants and branching yields (ca. 10-11%) for thermal unimolecular decay of MECI to conventional and roaming products under laboratory and atmospheric conditions, consistent with the estimated experimental yield (ca. 7%).

Plain Language vs Standard Format for Youth Understanding of COVID-19 Recommendations: A Randomized Clinical Trial.

Importance: To ensure that youths can make informed decisions about their health, it is important that health recommendations be presented for understanding by youths. Objective: To compare understanding, accessibility, usability, satisfaction, intention to implement, and preference of youths provided with a digital plain language recommendation (PLR) format vs the original standard language version (SLV) of a health recommendation. Design, Setting, and Participants: This pragmatic, allocation-concealed, blinded, superiority randomized clinical trial included individuals from any country who were 15 to 24 years of age, had internet access, and could read and understand English. The trial was conducted from May 27 to July 6, 2022, and included a qualitative component. Interventions: An online platform was used to randomize youths in a 1:1 ratio to an optimized digital PLR or SLV format of 1 of 2 health recommendations related to the COVID-19 vaccine; youth-friendly PLRs were developed in collaboration with youth partners and advisors. Main Outcomes and Measures: The primary outcome was understanding, measured as the proportion of correct responses to 7 comprehension questions. Secondary outcomes were accessibility, usability, satisfaction, preference, and intended behavior. After completion of the survey, participants indicated their interest in completing a 1-on-1 semistructured interview to reflect on their preferred digital format (PLR or SLV) and their outcome assessment survey response. Results: Of the 268 participants included in the final analysis, 137 were in the PLR group (48.4% female) and 131 were in the SLV group (53.4% female). Most participants (233 [86.9%]) were from North and South America. No significant difference was found in understanding scores between the PLR and SLV groups (mean difference, 5.2%; 95% CI, -1.2% to 11.6%; P = .11). Participants found the PLR to be more accessible and usable (mean difference, 0.34; 95% CI, 0.05-0.63) and satisfying (mean difference, 0.39; 95% CI, 0.06-0.73) and had a stronger preference toward the PLR (mean difference, 4.8; 95% CI, 4.5-5.1 [4.0 indicated a neutral response]) compared with the SLV. No significant difference was found in intended behavior (mean difference, 0.22 (95% CI, -0.20 to 0.74). Interviewees (n = 14) agreed that the PLR was easier to understand and generated constructive feedback to further improve the digital PLR. Conclusions and Relevance: In this randomized clinical trial, compared with the SLV, the PLR did not produce statistically significant findings in terms of understanding scores. Youths ranked it higher in terms of accessibility, usability, and satisfaction, suggesting that the PLR may be preferred for communicating health recommendations to youths. The interviews provided suggestions for further improving PLR formats. Trial Registration: ClinicalTrials.gov Identifier: NCT05358990.