Implementation and Evaluation of a mHealth-Based Community Health Worker Feedback Loop for Hispanics with and at Risk for Diabetes.

BACKGROUND: Gaps in accessibility and communication hinder diabetes care in poor communities. Combining mobile health (mHealth) and community health workers (CHWs) into models to bridge these gaps has great potential but needs evaluation. OBJECTIVE: To evaluate a mHealth-based, Participant-CHW-Clinician feedback loop in a real-world setting. DESIGN: Quasi-experimental feasibility study with intervention and usual care (UC) groups. PARTICIPANTS: A total of 134 participants (n = 67/group) who were all low-income, uninsured Hispanics with or at-risk for type 2 diabetes. INTERVENTION: A 15-month study with a weekly to semimonthly mHealth Participant-CHW-Clinician feedback loop to identify participant issues and provide participants monthly diabetes education via YouTube. MAIN MEASURES: We used pre-defined feasibility measures to evaluate our intervention: (a) implementation, the execution of feedback loops to identify and resolve participant issues, and (b) efficacy, intended effects of the program on clinical outcomes (baseline to 15-month HbA1c, systolic blood pressure (SBP), diastolic blood pressure (DBP), and weight changes) for each group and their subgroups (at-risk; with diabetes, including uncontrolled (HbA1c ≥ 7%)). KEY RESULTS: CHWs identified 433 participant issues (mean = 6.5 ± 5.3) and resolved 91.9% of these. Most issues were related to supplies, 26.3% (n = 114); physical health, 23.1% (n = 100); and medication access, 20.8% (n = 90). Intervention participants significantly improved HbA1c (- 0.51%, p = 0.03); UC did not (- 0.10%, p = 0.76). UC DBP worsened (1.91 mmHg, p < 0.01). Subgroup analyses revealed HbA1c improvements for uncontrolled diabetes (intervention: - 1.59%, p < 0.01; controlled: - 0.72, p = 0.03). Several variables for UC at-risk participants worsened: HbA1c (0.25%, p < 0.01), SBP (4.05 mmHg, p < 0.01), DBP (3.21 mmHg, p = 0.01). There were no other significant changes for either group. CONCLUSIONS: A novel mHealth-based, Participant-CHW-Clinician feedback loop was associated with improved HbA1c levels and identification and resolution of participant issues. UC individuals had several areas of clinical deterioration, particularly those at-risk for diabetes, which is concerning for progression to diabetes and disease-related complications. CLINICAL TRIAL: NCT03394456, accessed at https://clinicaltrials.gov/ct2/show/NCT03394456.

Associations of regular consumption of breakfast, lunch and dinner with Body Mass Index during adolescence: longitudinal findings by weight status among the Eating and Activity over Time 2010-2018 cohort.

OBJECTIVE: To examine how the associations between meal consumption and BMI over 8 years differ by weight status in a sample of adolescents. DESIGN: Longitudinal, population-based study. Breakfast, lunch and dinner consumption and BMI were self-reported. Linear regressions were used to examine how the associations between meal consumption and BMI differed by weight status. SETTING: Adolescents in the Minneapolis/St. Paul metropolitan area. PARTICIPANTS: Adolescents (n 1,471) were surveyed as part of the EAT 2010-2018 in 2009-2010 (Mage = 14·3 years) and 2017-2018 (Mage = 22·0 years). RESULTS: The prevalence of regular breakfast, lunch and dinner consumption (≥ 5 times/week) ranged from 45 to 65 %, 75 to 89 % and 76 to 94 %, respectively, depending on weight status category. Among adolescents with a sex- and age-specific BMI < 15th percentile, regular consumptions of breakfast, lunch and dinner during adolescence were positively associated with BMI in emerging adulthood compared with irregular consumption of breakfast, lunch and dinner (<5 times/week) after adjustment for socio-demographic characteristics (ß = 5·43, ß = 5·39 and ß = 6·46, respectively; all P-values <0·01). Among adolescents in the BMI 15-85th and 85-95th percentiles, regular consumptions of breakfast, lunch and dinner were positively associated with BMI but to a lesser extent (P-values <0·01). For participants with a BMI ≥ 95th percentile, regular consumptions of breakfast, lunch and dinner were positively associated with BMI, but the associations were not statistically significant (P-values > 0·05). CONCLUSIONS: The relationship between meal consumption during adolescence and BMI in emerging adulthood differs by adolescent weight status. Future studies should investigate underlying factors related to meal consumption routines and BMI.

Exploring Factors Associated With Accelerometer Validity Among Ethnically Diverse Toddlers.

PURPOSE: Studying physical activity in toddlers using accelerometers is challenging due to noncompliance with wear time (WT) and activity log (AL) instructions. The aims of this study are to examine relationships between WT and AL completion and (1) demographic and socioeconomic variables, (2) parenting style, and (3) whether sedentary time differs by AL completion. METHODS: Secondary analysis was performed using baseline data from a community wellness program randomized controlled trial for parents with toddlers (12-35 mo). Parents had toddlers wear ActiGraph wGT3x accelerometers and completed ALs. Valid days included ≥600-minute WT. Analysis of variance and chi-square analyses were used. RESULTS: The sample (n = 50) comprised racial and ethnically diverse toddlers (mean age = 27 mo, 58% male) and parents (mean age = 31.7 y, 84% female). Twenty-eight families (56%) returned valid accelerometer data with ALs. Participants in relationships were more likely to complete ALs (P < .05). Toddler sedentary time did not differ between those with ALs and those without. CONCLUSIONS: We found varied compliance with WT instructions and AL completion. Returned AL quality was poor, presenting challenges in correctly characterizing low-activity counts to improve internal validity of WT and physical activity measures. Support from marital partners may be important for adherence to study protocols.

The Bead Maze Hand Function Test for Children.

IMPORTANCE: There is a need for a pediatric hand function test that can be used to objectively assess movement quality. We have developed a toy-based test, the Bead Maze Hand Function (BMHF) test, to quantify how well a child performs an activity. This is achieved by assessing the control of forces applied while drawing a bead over wires of different complexity. OBJECTIVE: To study the psychometric properties of the BMHF test and understand the influence of age and task complexity on test measures. DESIGN: A cross-sectional, observational study performed in a single visit. SETTING: Clinical research laboratory. PARTICIPANTS: Twenty-three participants (ages 4-15 yr) were recruited locally. They were typically developing children with no illness or conditions that affected their movement. Interventions/Assessments: Participants performed the BMHF test and the Box and Block test with both hands. OUTCOMES AND MEASURES: Total force and completion time were examined according to age and task complexity using a linear mixed-effects model. We calculated intraclass correlation coefficients to measure interrater reliability of the method and estimated concurrent validity using the Box and Block test. RESULTS: Total force and completion time decreased with age and depended on task complexity. The total force was more sensitive to task complexity. The Box and Block score was associated with BMHF completion time but not with total force. We found excellent interrater reliability. CONCLUSIONS AND RELEVANCE: A familiar toy equipped with hidden sensors provides a sensitive tool to assess a child's typical hand function. Plain-Language Summary: We developed the Bead Maze Hand Function (BMHF) test to determine how well a child performs an activity with their hands. The BMHF test is a toy equipped with hidden sensors. Twenty-three typically developing children with no illnesses or conditions that affected their hand movement participated in the study. We asked the children to perform the BMHF test with both hands. Our study found that occupational therapists can reliably use the BMHF test to assess a child's hand function.

Enantioselective Synthesis of α-Aryl Ketones by a Cobalt-Catalyzed Semipinacol Rearrangement.

A highly enantioselective cobalt-catalyzed semipinacol rearrangement of symmetric α,α-diarylallylic alcohols is disclosed. A chiral cobalt-salen catalyst generates a highly electrophilic carbocation surrogate following hydrogen atom transfer and radical-polar crossover steps. This methodology provides access to enantioenriched α-aryl ketones through invertive displacement of a cobalt(IV) complex during 1,2-aryl migration. A combination of readily available reagents, silane and N-fluoropyridinium oxidant, are used to confer this type of reactivity. An exploration into the effect of aryl substitution revealed the reaction tolerates para- and meta-halogenated, mildly electron-rich and electron-poor aromatic rings with excellent enantioselectivities and yields. The yield of the rearrangement diminished with highly electron-rich aryl rings whereas very electron-deficient and ortho-substituted arenes led to poor enantiocontrol. A Hammett analysis demonstrated the migratory preference for electron-rich aromatic rings, which is consistent with the intermediacy of a phenonium cation.

Associations of positive childhood experiences with binge-eating disorder characteristics and intuitive eating among college students.

Childhood experiences encompass both adverse and positive childhood events. Adverse childhood experiences are positively associated with binge-eating disorder characteristics and inversely associated with intuitive eating in adults. However, to what extent positive childhood experiences (PCEs) are associated with binge-eating disorder characteristics and intuitive eating remains unclear. This study examined the associations of cumulative and individual PCEs with binge-eating disorder characteristics and intuitive eating among college students. Data were collected from 828 college students in 2022 (54.5% female, Mage 20.9 ± 2.6 years). PCEs were assessed using the Benevolent Childhood Experiences scale. Binge-eating disorder characteristics were assessed with the Questionnaire on Eating and Weight Patterns-5. Intuitive eating was assessed with the Intuitive Eating Scale-2. Associations of PCEs with binge-eating disorder characteristics and intuitive eating were examined using modified Poisson regressions and linear regressions. PCEs were cumulatively associated with binge-eating disorder characteristics and intuitive eating (p for trend <.05). College students in the low PCEs category (0-4 PCEs) had 1.37-1.92 times the prevalence of binge-eating disorder characteristics and had 3.89 points lower intuitive eating score than those in the high PCEs category (9-10 PCEs). Among the individual PCEs, intrapersonal PCE (i.e., feeling comfortable with oneself during childhood) was associated with both a lower prevalence of binge-eating disorder characteristics (aPR = 0.56-0.76) and a higher score of intuitive eating (adjusted ß = 1.87, 95% CI = 1.28-2.46) after adjustment for sociodemographic variables. Findings from this study suggest that PCEs may play a role in eating behaviors of college students. Future studies with nationally representative samples should prospectively examine associations of PCEs with binge-eating disorder characteristics and intuitive eating and explore the underlying mechanisms of the associations between PCEs and eating behaviors.

Cobalt-Catalyzed Wagner-Meerwein Rearrangements with Concomitant Nucleophilic Hydrofluorination.

We report a cobalt-catalyzed Wagner-Meerwein rearrangement of gem-disubstituted allylarenes that generates fluoroalkane products with isolated yields up to 84 %. Modification of the counteranion of the N-fluoropyridinium oxidant suggests the substrates undergo nucleophilic fluorination during the reaction. Subjecting the substrates to other known metal-mediated hydrofluorination procedures did not lead to observable 1,2-aryl migration. Thus, indicating the unique ability of these cobalt-catalyzed conditions to generate a sufficiently reactive electrophilic intermediate capable of promoting this Wagner-Meerwein rearrangement.

Long-Term Effectiveness of the TIME Intervention to Improve Diabetes Outcomes in Low-Income Settings: a 2-Year Follow-Up.

BACKGROUND: We previously found that a 6-month multidimensional diabetes program, TIME (Telehealth-Supported, Integrated Community Health Workers, Medication-Access) resulted in improved clinical outcomes. OBJECTIVE: To follow TIME participant clinical outcomes for 24 months PARTICIPANTS: Low-income Latino(a)s with type 2 diabetes DESIGN AND INTERVENTION: We collected post-intervention clinical data for five cohorts (n = 101, mean n = 20/cohort) who participated in TIME programs from 2018 to 2020 in Houston, Texas. MAIN MEASURES: We gathered HbA1c (primary outcome), weight, body mass index (BMI), and blood pressure data at baseline, 6 months (intervention end), and semiannually thereafter until 24 months after baseline to assess sustainability. We also evaluated participant loss to follow-up until 24 months. KEY RESULTS: Participants decreased HbA1c levels during the intervention (p < 0.0001) and maintained these improvements at each timepoint from baseline to 24 months (p range: < 0.0001 to 0.015). Participants reduced blood pressure levels during TIME and maintained these changes at each timepoint from baseline until 18 months (systolic p range < 0.0001 to 0.0005, diastolic p range: < 0.0001 to 0.008) but not at 24 months (systolic: p = 0.065; diastolic: p = 0.85). There were no significant weight changes during TIME or post-intervention: weight (p range = 0.07 to 0.77), BMI (p range = 0.11 to 0.71). Attrition rates (loss to follow-up during the post-intervention period) were 5.9% (6 months), 24.8% (12 months), 35.6% (18 months), and 41.8% (24 months). CONCLUSIONS: It is possible for vulnerable populations to maintain long-term glycemic and blood pressure improvements using a multiple dimensional intervention. Attrition rates rose over time but show promise given the majority of post-intervention timepoints occurred during the COVID-19 pandemic when low-income populations were most susceptible to suboptimal healthcare access. Future studies are needed to evaluate longitudinal outcomes of diabetes interventions conducted by local clinics rather than research teams.

Metallaphotoredox-catalysed sp(3)-sp(3) cross-coupling of carboxylic acids with alkyl halides.

In the past 50 years, cross-coupling reactions mediated by transition metals have changed the way in which complex organic molecules are synthesized. The predictable and chemoselective nature of these transformations has led to their widespread adoption across many areas of chemical research. However, the construction of a bond between two sp(3)-hybridized carbon atoms, a fundamental unit of organic chemistry, remains an important yet elusive objective for engineering cross-coupling reactions. In comparison to related procedures with sp(2)-hybridized species, the development of methods for sp(3)-sp(3) bond formation via transition metal catalysis has been hampered historically by deleterious side-reactions, such as ß-hydride elimination with palladium catalysis or the reluctance of alkyl halides to undergo oxidative addition. To address this issue, nickel-catalysed cross-coupling processes can be used to form sp(3)-sp(3) bonds that utilize organometallic nucleophiles and alkyl electrophiles. In particular, the coupling of alkyl halides with pre-generated organozinc, Grignard and organoborane species has been used to furnish diverse molecular structures. However, the manipulations required to produce these activated structures is inefficient, leading to poor step- and atom-economies. Moreover, the operational difficulties associated with making and using these reactive coupling partners, and preserving them through a synthetic sequence, has hindered their widespread adoption. A generically useful sp(3)-sp(3) coupling technology that uses bench-stable, native organic functional groups, without the need for pre-functionalization or substrate derivatization, would therefore be valuable. Here we demonstrate that the synergistic merger of photoredox and nickel catalysis enables the direct formation of sp(3)-sp(3) bonds using only simple carboxylic acids and alkyl halides as the nucleophilic and electrophilic coupling partners, respectively. This metallaphotoredox protocol is suitable for many primary and secondary carboxylic acids. The merit of this coupling strategy is illustrated by the synthesis of the pharmaceutical tirofiban in four steps from commercially available starting materials.

How the future of the global forest sink depends on timber demand, forest management, and carbon policies.

Deforestation has contributed significantly to net greenhouse gas emissions, but slowing deforestation, regrowing forests and other ecosystem processes have made forests a net sink. Deforestation will still influence future carbon fluxes, but the role of forest growth through aging, management, and other silvicultural inputs on future carbon fluxes are critically important but not always recognized by bookkeeping and integrated assessment models. When projecting the future, it is vital to capture how management processes affect carbon storage in ecosystems and wood products. This study uses multiple global forest sector models to project forest carbon impacts across 81 shared socioeconomic (SSP) and climate mitigation pathway scenarios. We illustrate the importance of modeling management decisions in existing forests in response to changing demands for land resources, wood products and carbon. Although the models vary in key attributes, there is general agreement across a majority of scenarios that the global forest sector could remain a carbon sink in the future, sequestering 1.2-5.8 GtCO2e/yr over the next century. Carbon fluxes in the baseline scenarios that exclude climate mitigation policy ranged from -0.8 to 4.9 GtCO2e/yr, highlighting the strong influence of SSPs on forest sector model estimates. Improved forest management can jointly increase carbon stocks and harvests without expanding forest area, suggesting that carbon fluxes from managed forests systems deserve more careful consideration by the climate policy community.

Global mitigation potential of carbon stored in harvested wood products.

Carbon stored in harvested wood products (HWPs) can affect national greenhouse gas (GHG) inventories, in which the production and end use of HWPs play a key role. The Intergovernmental Panel on Climate Change (IPCC) provides guidance on HWP carbon accounting, which is sensitive to future developments of socioeconomic factors including population, income, and trade. We estimated the carbon stored within HWPs from 1961 to 2065 for 180 countries following IPCC carbon-accounting guidelines, consistent with Food and Agriculture Organization of the United Nations (FAOSTAT) historical data and plausible futures outlined by the shared socioeconomic pathways. We found that the global HWP pool was a net annual sink of 335 Mt of CO2 equivalent (CO2e)⋅y-1 in 2015, offsetting substantial amounts of industrial processes within some countries, and as much as 441 Mt of CO2e⋅y-1 by 2030 under certain socioeconomic developments. Furthermore, there is a considerable sequestration gap (71 Mt of CO2e⋅y-1 of unaccounted carbon storage in 2015 and 120 Mt of CO2e⋅y-1 by 2065) under current IPCC Good Practice Guidance, as traded feedstock is ineligible for national GHG inventories. However, even under favorable socioeconomic conditions, and when accounting for the sequestration gap, carbon stored annually in HWPs is <1% of global emissions. Furthermore, economic shocks can turn the HWP pool into a carbon source either long-term-e.g., the collapse of the USSR-or short-term-e.g., the US economic recession of 2008/09. In conclusion, carbon stored within end-use HWPs varies widely across countries and depends on evolving market forces.

A staged approach to address youth unresponsive to initial obesity intervention: a randomized clinical trial.

BACKGROUND/OBJECTIVE: Maintenance interventions inherently require BMI improvement to maintain. This overlooks individuals initially unresponsive to obesity interventions. Staged pediatric clinical treatment guidelines were adapted to the school setting to develop an escalated treatment option for individuals initially unresponsive. This staged randomized controlled trial examined differences between escalated treatment (Take CHARGE!) and a maintenance program (PE Planners). Take CHARGE was hypothesized to have greater improvements in BMI as a percentage of the 95th BMI Percentile (%BMIp95) than PE Planners. SUBJECTS/METHODS: From 2018 to 2020, 171 middle and high schoolers (BMI Percentile ≥ 85) were recruited from a Houston school district to participate in a staged obesity intervention in their physical education (PE) class. After receiving a semester-long intensive lifestyle intervention (ILI) with established efficacy, all participants were randomized to Take CHARGE (n = 85) or PE Planners (n = 86). Take CHARGE escalated the behavioral treatment of obesity received in ILI with more frequent individual sessions, additional opportunities for parental and school staff involvement, and increased mentorship from trained college students. PE Planners allowed participants to decide how they wanted to be active in PE class. Mixed linear modeling examined %BMIp95 overtime between groups. This trial was registered at ClinicalTrials.gov (#NCT04362280). RESULTS: Participants were 13.63 ± 1.32 years old; 59% were female, and 85% were Hispanic. Among those initially unresponsive to ILI, Take CHARGE had significantly greater decreases in %BMIp95 than PE Planners (ß = -0.01, p < 0.01). Conversely, among those initially responsive, Take CHARGE had significantly smaller decreases in %BMIp95 than PE Planners (ß = 0.02, p < 0.05). Intention-to-treat analysis had similar results. CONCLUSIONS: Participant outcomes in semester two differed based on initial response. Individuals responsive to initial intervention were most likely to benefit from a maintenance intervention and those initially unresponsive benefited more from escalated treatment. This indicates the need for staged intervention protocols to better address obesity in the school setting.

Exploring qualities of ethnically diverse parents related to the healthy home environment of toddlers.

Parents serve as role models and household policy makers for their children's home social environment. Also, parents may influence the home physical environment through the provision of resources to support their children's dietary, activity, and sleep behaviors. Understanding the parental characteristics related to children's home environment may allow for tailoring obesity interventions to families' needs. This study aimed to explore parental qualities (general parenting styles, parent feeding practices, and parental BMI) related to healthy home food, physical activity, media and sleep environment of toddlers. A total of 50 multi-ethnic parents with toddler age children who were enrolled in a randomized pilot study of a wellness program completed the Structure and Control in Parent Feeding (SCPF) questionnaire and Comprehensive General Parenting Questionnaire (CGPQ). Parental BMI was calculated using self-reported weight and height data. The Healthy Home Survey, the Home Food Inventory, the Sleep Environment Questionnaire, and items developed for this study were standardized and summed to create home food, physical activity, screen media, and sleep environment scores; high scores reflected healthier environments. To examine the relationships between parental qualities and the home environment, Pearson's correlation test was performed. Parental BMI and overall healthy home environment were inversely associated (r = -0.306; p = 0.032). Structure in general parenting and parental feeding practice were positively correlated with the overall healthy home environment (r = 0.336; p = 0.026) and healthy home food environment (r = 0.415; p = 0.003), respectively. The coercive control general parenting was inversely related to overall healthy home environment score (r = -0.333; p = 0.022). Based on the findings from this study, parents who provide clear communication, set consistent rules, avoid pressure to control their child's behavior, and have lower BMI tend to live in a home environment that support children's health behaviors.

Synthesis of Indoloquinolines: An Intramolecular Cyclization Leading to Advanced Perophoramidine-Relevant Intermediates.

The bioactive natural product perophoramidine has proved a challenging synthetic target. An alternative route to its indolo[2,3-b]quinolone core structure involving a N-chlorosuccinimde-mediated intramolecular cyclization reaction is reported. Attempts to progress towards the natural product are also discussed with an unexpected deep-seated rearrangement of the core structure occurring during an attempted iodoetherification reaction. X-ray crystallographic analysis provides important analytical confirmation of assigned structures.

Difluorocarbene Generation from TMSCF3: Kinetics and Mechanism of NaI-Mediated and Si-Induced Anionic Chain Reactions.

The mechanism of CF2 transfer from TMSCF3 (1), mediated by TBAT (2-12 mol %) or by NaI (5-20 mol %), has been investigated by in situ/stopped-flow 19F NMR spectroscopic analysis of the kinetics of alkene difluorocyclopropanation and competing TFE/c-C3F6/homologous perfluoroanion generation, 13C/2H KIEs, LFERs, CF2 transfer efficiency and selectivity, the effect of inhibitors, and density functional theory (DFT) calculations. The reactions evolve with profoundly different kinetics, undergoing autoinhibition (TBAT) or quasi-stochastic autoacceleration (NaI) and cogenerating perfluoroalkene side products. An overarching mechanism involving direct and indirect fluoride transfer from a CF3 anionoid to TMSCF3 (1) has been elucidated. It allows rationalization of why the NaI-mediated process is more effective for less-reactive alkenes and alkynes, why a large excess of TMSCF3 (1) is required in all cases, and why slow-addition protocols can be of benefit. Issues relating to exothermicity, toxicity, and scale-up are also noted.

Levels of adherence needed to achieve significant weight loss.

BACKGROUND/OBJECTIVES: Positive associations have been found between adherence and weight loss in behavioral weight-management interventions. However, less attention has been given to the level of adherence needed to reach clinically significant weight loss. This study examined the levels of adherence associated with a ≥ 5% - < 10% or ≥ 10% weight loss in a community-based, intensive behavioral weight management program, Weight Watchers® (WW), which included three modes of access: (1) 24-weekly WW meetings over 6 months, (2) the WW member website, and (3) the WW mobile application. METHODS: A total of 292 participants were randomized to a WW (n = 147) or a self-help (SH) (n = 145) condition. To assess the impact of adherence, only participants in the WW condition were included in analyses (n = 147). Adherence was defined as use of the three modes of access. Measured heights and weights were obtained at baseline and 6 months. Receiver-operating characteristic curve analyses were conducted to determine the minimal level of adherence associated with clinically significant weight loss. RESULTS: In a 6-month period, increased likelihood of achieving a weight loss ≥ 5% - < 10% was associated with attending approximately one-third (35.4%) of weekly meetings, use of the member website about 25% of days, and use of the mobile application 16.1% of days. Attendance at approximately two-thirds (64.5%) of meetings, use of the member website 41.6% of days, and use of the mobile application 14.7% of days were associated with a clinically significant weight loss of ≥ 10%. Meeting attendance was the strongest predictor of weight loss at 6 months. CONCLUSIONS: Although adherence to a behavioral weight management program was an important predictor of weight loss, extremely high levels were not needed to achieve clinically significant weight loss. These results are important to help patients and treatment providers understand realistic goals for weight management.

Anion-Initiated Trifluoromethylation by TMSCF3: Deconvolution of the Siliconate-Carbanion Dichotomy by Stopped-Flow NMR/IR.

The mechanism of CF3 transfer from R3SiCF3 (R = Me, Et, iPr) to ketones and aldehydes, initiated by M+X- (<0.004 to 10 mol %), has been investigated by analysis of kinetics (variable-ratio stopped-flow NMR and IR), 13C/2H KIEs, LFER, addition of ligands (18-c-6, crypt-222), and density functional theory calculations. The kinetics, reaction orders, and selectivity vary substantially with reagent (R3SiCF3) and initiator (M+X-). Traces of exogenous inhibitors present in the R3SiCF3 reagents, which vary substantially in proportion and identity between batches and suppliers, also affect the kinetics. Some reactions are complete in milliseconds, others take hours, and others stall before completion. Despite these differences, a general mechanism has been elucidated in which the product alkoxide and CF3- anion act as chain carriers in an anionic chain reaction. Silyl enol ether generation competes with 1,2-addition and involves protonation of CF3- by the α-C-H of the ketone and the OH of the enol. The overarching mechanism for trifluoromethylation by R3SiCF3, in which pentacoordinate siliconate intermediates are unable to directly transfer CF3- as a nucleophile or base, rationalizes why the turnover rate (per M+X- initiator) depends on the initial concentration (but not identity) of X-, the identity (but not concentration) of M+, the identity of the R3SiCF3 reagent, and the carbonyl/R3SiCF3 ratio. It also rationalizes which R3SiCF3 reagent effects the most rapid trifluoromethylation, for a specific M+X- initiator.

Compañeros: High School Students Mentor Middle School Students to Address Obesity Among Hispanic Adolescents.

INTRODUCTION: Promotoras, Hispanic community health workers, are frequently employed to promote health behavioral change with culturally bound Hispanic lifestyle behaviors. Peer health mentors have been used in schools to promote healthy nutrition and physical activity behaviors among students. This study investigates the efficacy of combining these 2 approaches by training high school health mentors, called compañeros, to engage Hispanic middle school students in a school-based obesity intervention as a strategy to promote and sustain reductions in standardized body mass index (zBMI). METHODS: High school compañeros were trained to participate in a 6-month obesity program alongside middle school students in Houston, Texas. Middle school students were randomized to participate in the program either with compañeros (n = 94) or without compañeros (n = 95). The intervention was conducted from 2013 through 2016 in 3 cohorts of students, 1 each school year. Students were followed for 12 months. The primary outcome was zBMI, which was analyzed at baseline, 6 months, and 12 months. RESULTS: Significant differences were found between conditions across time (F = 4.58, P = .01). After the 6-month intervention, students in the condition with compañeros had a larger decrease in zBMI (F = 6.94, P = .01) than students in the condition without compañeros. Furthermore, students who received the intervention with compañeros showed greater sustained results at 12 months (F = 7.65, P = .01). CONCLUSION: Using high school compañeros in an obesity intervention for Hispanic middle school students could be effective in promoting and maintaining reductions in zBMI.

Obesity status trajectory groups among elementary school children.

BACKGROUND: Little is known about patterns in the transition from healthy weight to overweight or obesity during the elementary school years. This study examined whether there were distinct body mass index (BMI) trajectory groups among elementary school children, and predictors of trajectory group membership. METHODS: This is a secondary analysis of 1651 elementary school children with complete biannual longitudinal data from kindergarten to the beginning of 5(th) grade. Heights and weights were measured by trained school nurses using standard procedures at the beginning and end of each school year for 11 consecutive assessments. Group-based trajectory clustering and multinomial logit modeling were conducted. RESULTS: When using BMIz score, six trajectory groups were identified revealing substantial consistency in BMIz score across time. When using a categorical variable separating overweight/obese children (BMI ≥ 85%ile) from the rest, five developmental trajectories (persistently non-overweight/obese weight: 51.1 %; early-onset overweight/obese: 9.2 %; late-onset overweight/obese: 9.7 %; becoming healthy weight: 8.2 %; and chronically overweight/obese: 21.8 %) were identified. When using a categorical variable separating obese children (BMI ≥ 95%ile) from the rest, three trajectories (persistently non-obese: 74.1 %, becoming obese: 12.8 %; and chronically obese: 13.2 %) were identified. For both cutoffs (≥ BMI percentile 85 % or 95 %), girls were more likely than boys to be classified in the persistently non-overweight and/or obese group (odds ratios (OR) ranged from 0.53 to 0.67); and Hispanic children and non-Hispanic Black children were more likely to be chronically overweight and/or obese than non-Hispanic White children (OR ranged from 1.57 to 2.44). Hispanic children were also more likely to become obese (OR: 1.84) than non-Hispanic White children when ≥ BMI percentile 95 % was used. CONCLUSIONS: Boys, Hispanic and non-Hispanic Black children were at higher risk of being overweight or obese throughout their elementary school years, supporting the need for obesity treatment. Post kindergarten and post second grade summer months were times when some children transitioned into overweight/obesity. It will be important to identify which behavioral factors (e.g., diet, physical activity, sedentary behaviors, and/or sleep) predisposed children to becoming overweight/obese, and whether these factors differ by time (Kindergarten versus second grade). If behavioral predisposing factors could be identified early, targeted obesity prevention should be offered.

Cation-Controlled Enantioselective and Diastereoselective Synthesis of Indolines: An Autoinductive Phase-Transfer Initiated 5-endo-trig Process.

A catalytic enantioselective approach to the synthesis of indolines bearing two asymmetric centers, one of which is all-carbon and quaternary, is described. This reaction proceeds with high levels of diastereoselectivity (>20:1) and high levels of enantioselectivity (up to 99.5:0.5 er) in the presence of CsOH·H2O and a quinine-derived ammonium salt. The reaction most likely proceeds via a delocalized 2-aza-pentadienyl anion that cyclizes either by a suprafacial electrocyclic mechanism, or through a kinetically controlled 5-endo-trig Mannich process. Density functional theory calculations are used to probe these two mechanistic pathways and lead to the conclusion that a nonpericyclic mechanism is most probable. The base-catalyzed interconversion of diastereoisomeric indolines in the presence of certain quaternary ammonium catalysts is observed; this may be rationalized as a cycloreversion-cyclization process. Mechanistic investigations have demonstrated that the reaction is initiated via a Makosza-like interfacial process, and kinetic analysis has shown that the reaction possesses a significant induction period consistent with autoinduction. A zwitterionic quinine-derived entity generated by deprotonation of an ammonium salt with the anionic reaction product is identified as a key catalytic species and the role that protonation plays in the enantioselective process outlined. We also propose that the reaction subsequently occurs entirely within the organic phase. Consequently, the reaction may be better described as a phase-transfer-initiated rather than a phase-transfer-catalyzed process; this observation may have implications for mechanistic pathways followed by other phase-transfer-mediated reactions.