High-Resolution Studies of Tropolone in the S 0 and S 1 Electronic States: Isotope Driven Dynamics in the Zero-Point Energy Levels

Rotationally resolved microwave (MW) and ultraviolet (UV) spectra of jet-cooled tropolone have been obtained in S0 and S1 electronic states using Fourier-transform microwave and UV-laser/molecular-beam spectrometers. In the ground electronic state, the MW spectra of all heavy-atom isotopomers including one O18 and four C13 isotopomers were observed in natural abundance. The OD isotopomer was obtained from isotopically enriched samples. The two lowest tunneling states of each isotopomer except O18 have been assigned. The observed inversion splitting for the OD isotopomer is 1523.227(5) MHz. For the asymmetric C13 structures, the magnitudes of tunneling-rotation interactions are found to diminish with decreasing distance between the heavy atom and the tunneling proton. In the limit of closest approach, the 0+ state of O18 was well fitted to an asymmetric rotor Hamiltonian, reflecting significant changes in the tautomerization dynamics. Comparisons of the substituted atom coordinates with theoretical predictions at the MP2/aug-cc-pVTZ level of theory suggest the localized 0+ and 0− wave functions of the heavier isotopes favor the C–OH and C=O forms of tropolone, respectively. The only exception occurs for the C13-OH and C13=O structures which correlate to the 0− and 0+ states, respectively. These preferences reflect kinetic isotope effects as quantitatively verified by the calculated zero-point energy differences between members of the asymmetric atom pairs. From rotationally resolved data of the 0+←0+ and 0−←0− bands in S1, line-shape fits have yielded Lorentzian linewidths that differ by 12.2(16) MHz over the 19.88(4)cm−1 interval in S1. The fluorescence decay rates together with previously reported quantum yield data give nonradiative decay rates of 7.7(5)×108 and 8.5(5)×108s−1 for the 0+ and 0− levels of the S1 state of tropolone

Impaired postprandial skeletal muscle vascular responses to a mixed meal challenge in normoglycaemic people with a parent with type 2 diabetes

Aims/hypothesis: Microvascular blood flow (MBF) increases in skeletal muscle postprandially to aid in glucose delivery and uptake in muscle. This vascular action is impaired in individuals who are obese or have type 2 diabetes. Whether MBF is impaired in normoglycaemic people at risk of type 2 diabetes is unknown. We aimed to determine whether apparently healthy people at risk of type 2 diabetes display impaired skeletal muscle microvascular responses to a mixed-nutrient meal. Methods: In this cross-sectional study, participants with no family history of type 2 diabetes (FH-) for two generations (n = 18), participants with a positive family history of type 2 diabetes (FH+; i.e. a parent with type 2 diabetes; n = 16) and those with type 2 diabetes (n = 12) underwent a mixed meal challenge (MMC). Metabolic responses (blood glucose, plasma insulin and indirect calorimetry) were measured before and during the MMC. Skeletal muscle large artery haemodynamics (2D and Doppler ultrasound, and Mobil-O-graph) and microvascular responses (contrast-enhanced ultrasound) were measured at baseline and 1 h post MMC. Results: Despite normal blood glucose concentrations, FH+ individuals displayed impaired metabolic flexibility (reduced ability to switch from fat to carbohydrate oxidation vs FH-; p \u3c 0.05) during the MMC. The MMC increased forearm muscle microvascular blood volume in both the FH- (1.3-fold, p \u3c 0.01) and FH+ (1.3-fold, p \u3c 0.05) groups but not in participants with type 2 diabetes. However, the MMC increased MBF (1.9-fold, p \u3c 0.01), brachial artery diameter (1.1-fold, p \u3c 0.01) and brachial artery blood flow (1.7-fold, p \u3c 0.001) and reduced vascular resistance (0.7-fold, p \u3c 0.001) only in FH- participants, with these changes being absent in FH+ and type 2 diabetes. Participants with type 2 diabetes displayed significantly higher vascular stiffness (p \u3c 0.001) compared with those in the FH- and FH+ groups; however, vascular stiffness did not change during the MMC in any participant group. Conclusions/interpretation: Normoglycaemic FH+ participants display impaired postprandial skeletal muscle macro- and microvascular responses, suggesting that poor vascular responses to a meal may contribute to their increased risk of type 2 diabetes. We conclude that vascular insulin resistance may be an early precursor to type 2 diabetes in humans, which can be revealed using an MMC

Complex and sustained quantum beating patterns in a classic IVR system: the 3¹5¹ Level in S₁ p-difluorobenzene

Using picosecond time-resolved photoelectron imaging we have studied the intramolecular vibrational energy redistribution (IVR) dynamics that occur following the excitation of the 3151 level which lies 2068 cm-1 above the S1 origin in p difluorobenzene. Our technique, which has superior time resolution to that of earlier studies but retains sufficient energy resolution to identify the behavior of individual vibrational states, enables us to determine six distinct beating periods in photoelectron intensity, only one of which has been observed previously. Analysis shows that the IVR dynamics are restricted among only a handful of vibrational levels, despite the relatively high excitation energy. This is deduced to be a consequence of the high symmetry and rigid structure of p-difluorobenzene

Perivascular Fat and the Microcirculation: Relevance to Insulin Resistance, Diabetes, and Cardiovascular Disease

Type 2 diabetes and its major risk factor, obesity, are a growing burden for public health. The mechanisms that connect obesity and its related disorders, such as insulin resistance, type 2 diabetes, and hypertension, are still undefined. Microvascular dysfunction may be a pathophysiologic link between insulin resistance and hypertension in obesity. Many studies have shown that adipose tissue-derived substances (adipokines) interact with (micro)vascular function and influence insulin sensitivity. In the past, research focused on adipokines from perivascular adipose tissue (PVAT). In this review, we focus on the interactions between adipokines, predominantly from PVAT, and microvascular function in relation to the development of insulin resistance, diabetes, and cardiovascular disease

‘Measuring’ Physical Literacy and Related Constructs: A Systematic Review of Empirical Findings

BACKGROUND:The concept of physical literacy has received increased research and international attention recently. Where intervention programs and empirical research are gaining momentum, their operationalizations differ significantly.OBJECTIVE:The objective of this study was to inform practice in the measure/assessment of physical literacy via a systematic review of research that has assessed physical literacy (up to 14 June, 2017).METHODS:Five databases were searched using the Preferred Reporting Items for Systematic Reviews and Meta-Analyses for Protocols guidelines, with 32 published articles meeting the inclusion criteria. English-language, peer-reviewed published papers containing empirical studies of physical literacy were analyzed using inductive thematic analysis.RESULTS:Qualitative methods included: (1) interviews; (2) open-ended questionnaires; (3) reflective diaries; (4) focus groups; (5) participant observations; and (6) visual methods. Quantitative methods included: (1) monitoring devices (e.g., accelerometers); (2) observations (e.g., of physical activity or motor proficiency); (3) psychometrics (e.g., enjoyment, self-perceptions); (4) performance measures (e.g., exergaming, objective times/distances); (5) anthropometric measurements; and (6) one compound measure. Of the measures that made an explicit distinction: 22 (61%) examined the physical domain, eight (22%) the affective domain; five (14%) the cognitive domain; and one (3%) combined three domains (physical, affective, and cognitive) of physical literacy. Researchers tended to declare their philosophical standpoint significantly more in qualitative research compared with quantitative research.CONCLUSIONS:Current research adopts diverse often incompatible methodologies in measuring/assessing physical literacy. Our analysis revealed that by adopting simplistic and linear methods, physical literacy cannot be measured/assessed in a traditional/conventional sense. Therefore, we recommend that researchers are more creative in developing integrated philosophically aligned approaches to measuring/assessing physical literacy. Future research should consider the most recent developments in the field of physical literacy for policy formation

Ocorrência das estratégias de reparo para os fonemas plosivos, considerando o grau do desvio fonológico

OBJETIVO: verificar a ocorrência ou não de estratégias de reparo para os fonemas /b/, /d/, /k/ e /g/ e a relação destas estratégias com a gravidade do desvio fonológico. MÉTODO: selecionados 54 sujeitos com diagnóstico de desvio fonológico que apresentavam estratégias de reparo para as consoantes plosivas /b/, /d/, /k/ e /g/ nas posições de onset inicial e/ou medial, com emprego de 40% em seu sistema fonológico. Os dados foram submetidos à análise estatística por meio do programa Statistical Analysis System, versão 8.02, utilizando-se o Teste Exato de Fisher. O nível de significância adotado para os testes estatísticos foi de 5% (pPURPOSE: to check the occurrence of repair strategies for the phonemes /b/, /d/, /k/ e /g/ and their relation to the severity of phonological disorder. METHOD: 54 subjects were selected with a diagnosis of phonological disorder who had repair strategies for the stops / b /, / d /, / k / and / g / in the onset positions (initial and / or medial), with 40% of employment in their phonological systems. Data were statistically analyzed using the Statistical Analysis System program, version 8.02, and using the Fisher Test. The level of significance was 5% (p< 0.05). RESULTS: there was a significant difference for / b / with greater frequency of devoicing in children from moderate-severe and severe degrees, and backing and use of two or more strategies in the severe degree. Statistically significant difference for /d/ with greater frequency of backing in the subjects with mild degree, of devoicing and use of two or more strategies in patients with moderate-severe degree, and devoicing in those with severe degree. CONCLUSION: the more complex in terms of acquisition and production are the stops, most repair strategies are used. And yet, the greater is the degree of phonological disorder, the greater is the number of times where these strategies are used, showing that the child has less phonological knowledge