Ligand effects, solvent cooperation, and large kinetic solvent deuterium isotope effects in gold(I)-catalyzed intramolecular alkene hydroamination.

Kinetic studies on the intramolecular hydroamination of protected variants of 2,2-diphenylpent-4-en-1-amine were carried out under a variety of conditions with cationic gold catalysts supported by phosphine ligands. The impact of ligand on gold, protecting group on nitrogen, and solvent and additive on reaction rates was determined. The most effective reactions utilized more Lewis basic ureas, and more electron-withdrawing phosphines. A DCM/alcohol cooperative effect was quantified, and a continuum of isotope effects was measured with low KIE's in the absence of deuterated alcoholic solvent, increasing to large solvent KIE's when comparing reactions in pure MeOH to those in pure MeOH-d4. The effects are interpreted both within the context of a classic gold π-activation/protodeauration mechanism and a general acid-catalyzed mechanism without intermediate gold alkyls.

The nature and extent of outdoor alcohol marketing in Wellington, New Zealand: a longitudinal audit and spatio-temporal analysis of outdoor alcohol marketing.

AIM: exposure to alcohol marketing is associated with increased consumption. We aimed to (i) measure the nature and extent of outdoor alcohol marketing within a high-density urban neighbourhood and (ii) examine temporal and spatial trends in alcohol marketing. METHODS: this study used a longitudinal design to monitor paid advertising in public spaces over two 10-week periods in Wellington, New Zealand (Nov-Jan 2020-2021, Nov-Jan 2021-2022). The data were collected on-foot following an established route once a week using a phone camera, which also recorded gps data of ad locations. Temporal and spatial trends in alcohol ad prevalence were assessed. RESULTS: over the study period, 13% (n = 1619) of all ads (n = 12,472) were for alcohol. Alcohol ads were predominately for spirits (29%), ready-to-drink (27%) and beer (23%). Almost half of all alcohol ads (49%) did not contain a responsible consumption message, while those with a message were de-emphasized relative to promotional features. A temporal trend was observed in 2020, whereby alcohol marketing decreased over the summer, but this trend was not reflected in 2021. Alcohol ads were more likely than non-alcohol ads to be placed in premium positions on roads of high pedestrian and motor vehicle traffic. CONCLUSION: alcohol marketing is common in urban centres. Local and central government policy could substantially reduce the levels of alcohol marketing exposure via outdoor marketing.

Food tax policies in Pacific Island Countries and Territories: systematic policy review.

OBJECTIVE: To systematically identify and review food taxation policy changes in Pacific Island Countries and Territories (PICTs). DESIGN: Food taxation polices, regarding excise taxes and tariffs applied from 2000 to 2020 in twenty-two PICTs, and their key characteristics were reviewed. The search was conducted using databases, government legal repositories and broad-based search engines. Identified documents for screening included legislation, reports, academic literature, news articles and grey literature. Key informants were contacted from each PICT to retrieve further data and confirm results. Results were analysed by narrative synthesis. SETTING: Noncommunicable diseases (NCD) are the leading cause of premature death in PICTs and in many jurisdictions globally. An NCD crisis has been declared in the Pacific, and food taxation policy has been recommended to address the dietary risk factors associated with. Progress is unclear. RESULTS: Of the twenty-two PICTs included in the study, fourteen had food taxation policies and five introduced excise taxes. Processed foods, sugar and salt were the main target of excise taxes. A total of eighty-four food taxation policy changes were identified across all food groups. There was a total of 279 taxes identified by food group, of which 85 % were tariffs and 15 % were excise taxes. Individual tax rates varied substantially. The predominant tax design was ad valorem, and this was followed by volumetric. CONCLUSIONS: A quarter of PICTs have introduced food excise taxes from 2000 to 2020. Further excise taxes, specifically tiered or nutrient-specific designs, could be introduced and more systematically applied to a broader range of unhealthy foods.

Situating reproductive coercion in the sociocultural context: An ecological model to inform research, practice, and policy in the United States.

Reproductive coercion (RC) can be conceptualized as any behavior that limits one's ability to make decisions about their reproductive health. Here, we broaden this definition to consider the impact of systemic and sociocultural factors on RC using an ecological model. Specifically, we use Bronfenbrenner's model as a framework for organizing the multilevel factors that influence reproductive coercion (RC) and its impacts on individual health. This paper is intended to offer a primer to historical, sociocultural, community, interpersonal, and individual processes that may interact to shape reproductive decision-making and its effect on individual health outcomes. We emphasize the importance of conceptualizing RC within the broader sociocultural and community context, and the potential implications for reproductive and sexual health research, clinical care, and policy in the United States.

Poor smoke-free status of airports in a country with a smoke-free goal: New Zealand.

BACKGROUND: To survey the smoke-free status of airports in New Zealand (NZ), a country with a smoke-free goal for 2025, and where public indoor areas are required to be smoke-free. METHODS: A cross-sectional survey of a convenience sample of airports with data collection on smoke-free signage, observed smoking behaviour, cigarette butt litter and designated smoking areas. RESULTS: A total of 23 airports were surveyed, including all those for the 10 most populous urban areas in NZ (82% of all airports with scheduled flights on the main islands). There were no smoke-free signs found at entrances/exits to the terminal building in 26% of airports, with a mean of 1.7 such signs per entrance/exit. Only one airport had any signage stating that all the grounds were smoke-free. Qualitatively, the signage was often small in size (<15 cm diameter). There was also ambiguity as to what the signage related to (indoors or outdoors). Observed smoking and vaping outside of the main entrances/exits was relatively uncommon, but the great majority of these sites (91%) had discarded cigarette butts present. Most airports (70%) had some form of designated or implied outdoor smoking area, with 38% of these areas being within 10 m distance of a terminal entrance/exit. CONCLUSIONS: Despite this country having a smoke-free goal, it has largely deficient smoke-free policies at its airports. There is a case to make airport grounds entirely smoke-free as part of an upgrade of the national smoke-free law.

Taxes and front-of-package labels improve the healthiness of beverage and snack purchases: a randomized experimental marketplace.

BACKGROUND: Sugar taxes and front-of-package (FOP) nutrition labelling systems are strategies to address diet-related non-communicable diseases. However, there is relatively little experimental data on how these strategies influence consumer behavior and how they may interact. This study examined the relative impact of different sugar taxes and FOP labelling systems on beverage and snack food purchases. METHODS: A total of 3584 Canadians 13 years and older participated in an experimental marketplace study using a 5 (FOP label condition) × 8 (tax condition) between-within group experiment. Participants received $5 and were presented with images of 20 beverages and 20 snack foods available for purchase. Participants were randomized to one of five FOP label conditions (no label; 'high in' warning; multiple traffic light; health star rating; nutrition grade) and completed eight within-subject purchasing tasks with different taxation conditions (beverages: no tax, 20% tax on sugar-sweetened beverages (SSBs), 20% tax on sugary drinks, tiered tax on SSBs, tiered tax on sugary drinks; snack foods: no tax, 20% tax on high-sugar foods, tiered tax on high-sugar foods). Upon conclusion, one of eight selections was randomly chosen for purchase, and participants received the product and any change. RESULTS: Compared to those who saw no FOP label, participants who viewed the 'high in' symbol purchased less sugar (- 2.5 g), saturated fat (- 0.09 g), and calories (- 12.6 kcal) in the beverage purchasing tasks, and less sodium (- 13.5 mg) and calories (- 8.9 kcal) in the food tasks. All taxes resulted in substantial reductions in mean sugars (- 1.4 to - 4.7 g) and calories (- 5.3 to - 19.8 kcal) purchased, and in some cases, reductions in sodium (- 2.5 to - 6.6 mg) and saturated fat (- 0.03 to - 0.08 g). Taxes that included 100% fruit juice ('sugary drink' taxes) produced greater reductions in sugars and calories than those that did not. CONCLUSIONS: This study expands the evidence indicating the effectiveness of sugar taxation and FOP labelling strategies in promoting healthy food and beverage choices. The results emphasize the importance of applying taxes to 100% fruit juice to maximize policy impact, and suggest that nutrient-specific FOP 'high in' labels may be more effective than other common labelling systems at reducing consumption of targeted nutrients.

Unified Enantioselective, Convergent Synthetic Approach toward the Furanobutenolide-Derived Polycyclic Norcembranoid Diterpenes: Synthesis of a Series of Ineleganoloids by Oxidation-State Manipulation of the Carbocyclic Core.

Late-stage synthetic efforts to advance the enatio- and diastereoselectively constructed [6,7,5,5]-fused tetracyclic scaffold toward the polycyclic norditerpenoid ineleganolide are disclosed. The described investigations focus on oxidation-state manipulation around the central cycloheptane ring. Computational evaluation of ground-state energies of dihydroineleganolide is used to rationalize empirical observations and provide insight for further synthetic development, enhancing the understanding of the conformational constraints of these compact polycyclic structures. Advanced synthetic manipulations generated a series of natural product-like compounds termed the ineleganoloids.

Beverage consumption and energy intake among Canadians: analyses of 2004 and 2015 national dietary intake data.

BACKGROUND: Among adults and children consuming Western diets, beverages are significant sources of free sugars, saturated fats, excess calories, and alcohol, with relevance to chronic disease risk. The impact of recent healthy eating policies and beverage market evolutions on population-level consumption patterns in Canada is unknown. The current study examined trends in intake of a range of beverage types among a nationally-representative sample of Canadians, with stratification by socio-demographic characteristics. METHODS: The 2004 (n = 34,775) and 2015 (n = 20,176) nutrition-focused cycles of the Canadian Community Health Surveys are cross-sectional surveys representative of the population of the 10 Canadian provinces. Based on a single multiple-pass 24-h dietary recall for each participant, fluids consumed as beverages were grouped into seven categories. Using linear regression, reported intake (volume, ml and energy, kcal) of each category was characterized over time and in relation to sex, age, ethnicity, income, body mass index (BMI), and province of residence. RESULTS: In 2015, Canadians reported consuming an average of 1806 ml (275 kcal) fluids as beverages per day, including: plain water 867 ml (0 kcal); other unsweetened beverages, e.g. coffee, 364 ml (6 kcal); sugar-sweetened beverages (SSBs) 204 ml (99 kcal); plain milk 132 ml (64 kcal); alcoholic drinks 120 ml (71 kcal); 100% juice 74 ml (34 kcal); and diet or low calorie beverages 44 ml (2 kcal). Differential consumption was observed across socio-demographic groups, with high consumption of sugary drinks (i.e., SSBs and 100% juice) and alcohol across groups. From 2004 to 2015, the reported volumes of beverages consumed decreased by 10% (energy: - 24%). With adjustment for socio-demographic characteristics, there were significant changes (p < 0.001) over time in intake of: 100% juice - 40% (- 38%); plain milk - 37% (- 35%); SSBs - 26% (- 20%); diet or low calorie beverages (- 46%); and other unsweetened beverages - 11% (- 42%). The volume of plain water consumed increased by 10% (p < 0.0001). Intake of alcoholic (volume and energy) and diet or light beverages did not change significantly. CONCLUSIONS: Lower intake of beverages was reported by Canadians in 2015 versus 2004, with a shift towards plain water. Consumption of sugary drinks decreased, but these beverages continue to contribute substantially to Canadians' overall energy intake. The findings underscore the need for policies to further reduce the consumption of sugary and alcoholic beverages, as well as calories from beverages.

Trends in sugary drinks in Canada, 2004 to 2015: a comparison of market sales and dietary intake data.

OBJECTIVE: The current study aimed to examine the correspondence between sales data and dietary recall data for sugary drinks in Canada. DESIGN: Repeat cross-sectional analysis of sales data for sugary drinks sold in Canada from 2004 to 2015 from two sources: GlobalData (GD) and Euromonitor (EM). Sugary drinks included ten beverage categories containing free sugars. Analyses examined sales volumes over time, with adjustment for population growth. National intake estimates were drawn from the 2004 and 2015 Canadian Community Health Survey (CCHS) Nutrition. SETTING: Canada. PARTICIPANTS: Not applicable. RESULTS: In 2015, daily per capita sugary drinks consumption was estimated as 356 ml (GD) and 443 ml (EM) from sales data sources, and as 277 ml from dietary recall data. Both sales data sources and dietary recall data indicated that per capita sugary drinks consumption decreased from 2004 to 2015, although the magnitude of this change differed: -23 % (GD), -17 % (EM) and -32 % (CCHS Nutrition). Market sales data showed similar trends among categories of sugary drinks, with decreases in sales of traditional beverage categories (e.g. carbonated soft drinks) and increases in novel categories (e.g. sugar-sweetened coffee). CONCLUSIONS: All data sources indicate a declining trend in sugary drinks consumption between 2004 and 2015, but with considerable differences in magnitude. Consumption estimates from sales data were substantially higher than estimates from dietary recall data, likely due to under-reporting of beverage intake through dietary recall and the inability of sales data to account for beverages sold but not consumed. Despite the observed decline, sugary drinks sales volumes remain high in Canada.

Development of a Unified Enantioselective, Convergent Synthetic Approach Toward the Furanobutenolide-Derived Polycyclic Norcembranoid Diterpenes: Asymmetric Formation of the Polycyclic Norditerpenoid Carbocyclic Core by Tandem Annulation Cascade.

An enantioselective and diastereoselective approach toward the synthesis of the tetracyclic scaffold of the furanobutenolide-derived polycyclic norditerpenoids is described. Focusing on synthetic efforts toward ineleganolide, the synthetic approach utilizes a palladium-catalyzed enantioselective allylic alkylation for the construction of the requisite chiral tertiary ether. A diastereoselective cyclopropanation-Cope rearrangement cascade enabled the convergent assembly of the ineleganolide [6,7,5,5]-tetracyclic scaffold. Investigation of substrates for this critical tandem annulation process is discussed along with synthetic manipulations of the [6,7,5,5]-tetracyclic scaffold and the attempted interconversion of the [6,7,5,5]-tetracyclic scaffold of ineleganolide to the isomeric [7,6,5,5]-core of scabrolide A and its naturally occurring isomers. Computational evaluation of ground-state energies of late-stage synthetic intermediates was used to guide synthetic development and aid in the investigation of the conformational rigidity of these highly constrained and compact polycyclic structures.

Evaluation of the online Beverage Frequency Questionnaire (BFQ).

BACKGROUND: The contribution of beverages to overall diet is of increasing interest to researchers and policymakers, particularly in terms of consumption of drinks high in added sugars; however, few tools to assess beverage intake have been developed and evaluated. This study aimed to evaluate the relative validity of a new online Beverage Frequency Questionnaire (BFQ) among young adults in Canada. METHODS: A cross-sectional relative validation study was conducted among young adults aged 16-30 years (n = 50). Participants completed a 17-item BFQ, a 7-day food record (7dFR), and a single-item measure of sugary drink intake. Pearson correlations and paired t-tests were used to evaluate correlation and agreement between the measures for 17 individual beverage categories, total drink consumption, total alcoholic beverage consumption, and two definitions of drinks with excess sugars. Cognitive interviews were conducted to examine participant interpretation and comprehensiveness of the BFQ. RESULTS: Estimates of beverage intake based on the BFQ and the 7dFR were highly correlated, specifically for the total number and volume of beverages consumed, total alcoholic beverage consumption, sugary drink intake, and each of the 17 beverage categories with 3 exceptions: coffee or tea with sugar or cream, specialty coffees, and hard alcohol with caloric mix. Paired t-tests between the BFQ and the 7dFR indicated that the average reported volume was significantly different only for sweetened fruit drinks. The single-item measure of sugary beverage intake was not significantly correlated with the 7dFR. Cognitive interviewing demonstrated high comprehension levels, and confirmed the appropriateness of the BFQ beverage categories and sizes. CONCLUSIONS: Overall, the results suggest that the BFQ performed well relative to a 7dFR and had high usability among this study population, indicating its promise for collecting population-level data on beverage intake, including sugar-sweetened beverages, which are known indicators of diet and health.

Sex differences in cortisol's regulation of affiliative behavior.

A contribution to a special issue on Hormones and Human Competition. A stress perspective is used to illuminate how competitive defeat and victory shape biology and behavior. We report a field study examining how change in cortisol following perceived defeat (vs. victory) in a competition-in this case, a dog agility competition-relates to affiliative behavior. Following competition, we measured cortisol change and the extent to which dog handlers directed affiliative behaviors toward their dogs. We found striking sex differences in affiliation. First, men were more affiliative toward their dogs after victory, whereas women were more affiliative after defeat. Second, the greater a female competitor's increase in cortisol, the more time she spent affiliating with her dog, whereas for men, the pattern was the exact opposite: the greater a male competitor's increase in cortisol, the less time he spent affiliating with his dog. This pattern suggests that, in the wake of competition, men and women's affiliative behavior may serve different functions-shared celebration for men; shared consolation for women. These sex differences show not only that men and women react very differently to victory and defeat, but also that equivalent changes in cortisol across the sexes are associated with strikingly different behavioral consequences for men and women.

Model Studies To Access the [6,7,5,5]-Core of Ineleganolide Using Tandem Translactonization-Cope or Cyclopropanation-Cope Rearrangements as Key Steps.

Recently, we reported a convergent cyclopropanation-Cope approach to the core of ineleganolide, which was the first disclosed synthesis of the core of the norditerpene natural product ineleganolide. In this complementary work, a model system for the core of ineleganolide has been prepared through a series of tandem cyclopropanation-Cope and translactonization-Cope rearrangements. Work with this model system has enriched our understanding of the cyclopropanation-Cope rearrangement sequence. Additionally, research into this model system has driven the development of tandem translactonization-Cope rearrangements.

'How many calories did I just eat?' An experimental study examining the effect of changes to serving size information on nutrition labels.

OBJECTIVE: To test modifications to nutrition label serving size information on understanding of energy (calorie) content among youth and young adults. DESIGN: Participants completed two online experiments. First, participants were randomly assigned to view a beverage nutrition label with a reference amount of per serving (250 ml), per container (473 ml) or a dual-column format with both reference amounts. Participants were then randomized to view a cracker nutrition label which specified a single serving in small font, a single serving in large font, or the number of servings per bag with single serving information below. In both experiments, participants estimated energy content. Logistic regression analysis modelled correct energy estimation. Finally, participants reported their preference for serving size display format. SETTING: Canada. SUBJECTS: Canadian youth and young adults (n 2008; aged 16-24 years). RESULTS: In experiment 1, participants randomized to view the nutrition label with per container or dual column were more likely to correctly identify energy content than those using per serving information (P<0·01). For experiment 2, the serving size display format had no association with correct energy estimation. The majority of participants (61·9 %) preferred the serving size format that included servings per package. CONCLUSIONS: Labelling foods with nutrition information using a serving size reference amount for the entire container increased understanding of energy content. Consumers prefer nutrition labels that include more prominently featured serving size information. Additional modifications that further improve consumers' accuracy should be examined. These results have direct implications for nutrition labelling policy.

Gold π-Complexes as Model Intermediates in Gold Catalysis.

Homogeneous gold catalysis has emerged as a powerful method for activating hydrocarbon double and triple bonds. Methodology development and computational studies have blossomed in the past 20 years. In contrast, experimental exploration of mechanisms and structure-reactivity relationships has gained traction only in the past 5 years. Recent developments in the synthesis of organometallic intermediates have revealed exciting new details about the mechanisms of gold catalysis. Central to these studies are the structure and reactivity of gold π-complexes. Following successes in structurally characterizing these key structures, advancements are gradually being made in placing them in the context of an overall catalytic cycle. As a result, a research field has emerged which is rich with potential for continued discovery and catalyst improvement.

Where Should We Eat? Lunch Source and Dietary Measures Among Youth During the School Week.

PURPOSE: To examine lunch sources during the school week among students and the associations with fruits and vegetable (F&V) and sugar-sweetened beverage (SSB) consumption. METHODS: Students (n = 23 680) from 43 Ontario, Canada, secondary schools completed a health behaviour survey in the Year 1 COMPASS study. Analysis used generalized linear mixed effects models. RESULTS: The most frequently reported lunch source was home (2.9 days per school week), then the school cafeteria (1.1) and fast-food places or restaurants (FFRs) (0.9). Eating a home lunch was associated with having less spending money, white ethnicity, and females; whereas cafeteria lunch was associated with more spending money, lower school grade, and females. A FFR lunch was associated with males, more spending money, and higher physical activity. Greater frequency of a home lunch was associated with greater F&V consumption. Greater frequency of a FFR lunch was associated with more frequent SSB consumption. Cafeteria lunches were associated with increases in both SSB and F&V. CONCLUSIONS: Eating a lunch obtained from outside of the home is a regular behaviour among students. Sources of school-week lunches may have an important influence on dietary intake among youth. These findings reinforce the need for strategies to promote healthier lunch sources and healthier food options.

Reversible inhibitor of p97, DBeQ, impairs both ubiquitin-dependent and autophagic protein clearance pathways.

A specific small-molecule inhibitor of p97 would provide an important tool to investigate diverse functions of this essential ATPase associated with diverse cellular activities (AAA) ATPase and to evaluate its potential to be a therapeutic target in human disease. We carried out a high-throughput screen to identify inhibitors of p97 ATPase activity. Dual-reporter cell lines that simultaneously express p97-dependent and p97-independent proteasome substrates were used to stratify inhibitors that emerged from the screen. N2,N4-dibenzylquinazoline-2,4-diamine (DBeQ) was identified as a selective, potent, reversible, and ATP-competitive p97 inhibitor. DBeQ blocks multiple processes that have been shown by RNAi to depend on p97, including degradation of ubiquitin fusion degradation and endoplasmic reticulum-associated degradation pathway reporters, as well as autophagosome maturation. DBeQ also potently inhibits cancer cell growth and is more rapid than a proteasome inhibitor at mobilizing the executioner caspases-3 and -7. Our results provide a rationale for targeting p97 in cancer therapy.

Toward a symphony of reactivity: cascades involving catalysis and sigmatropic rearrangements.

Catalysis and synthesis are intimately linked in modern organic chemistry. The synthesis of complex molecules is an ever evolving area of science. In many regards, the inherent beauty associated with a synthetic sequence can be linked to a certain combination of the creativity with which a sequence is designed and the overall efficiency with which the ultimate process is performed. In synthesis, as in other endeavors, beauty is very much in the eyes of the beholder. It is with this in mind that we will attempt to review an area of synthesis that has fascinated us and that we find extraordinarily beautiful, namely the combination of catalysis and sigmatropic rearrangements in consecutive and cascade sequences.

A unique Au-Ag-Au triangular motif in a trimetallic halonium dication: silver incorporation in a gold(I) catalyst.

As a result of explorations into the solution chemistry of silver/gold mixtures, a unique diphosphine trimetallic chloronium dication was discovered that incorporates silver-arene chelation and a triangular mixed gold/silver core in the solid state. Notably, it was isolated from a Celite prefiltered solution initially thought to be silver-free. The crystal structure also incorporates the coordination to silver of one fluorine atom of one SbF6(-) counterion. The structure was compared to two new, but well-precedented, phosphine digold chloride cations. DFT calculations supported significant silver-halide and silver-arene interactions in the mixed gold/silver complex and metallophilic interactions in all three complexes. Comparison of computed data revealed that the ωB97X-D functional, which has a long-range corrected hybrid with atom-atom dispersion corrections, gave a better fit to the experimental data compared with the PBE0 functional, which has previously failed to capture aurophilic interactions. Preliminary studies support the presence of the mixed gold/silver structure in solution.