Deporte extraescolar e inteligencia emocional en estudiantes de secundaria: efectos del tipo de agrupamiento deportivo y del sexo / Esporte extracurricular e inteligência emocional em estudantes do ensino médio: efeitos do tipo de agrupamento esportivo e gênero / Extracurricular sport and emotional intelligence in secondary school students: effects of the type of sports grouping and sex

El desarrollo de la inteligencia emocional se ha relacionado en estudios previos con la práctica deportiva y la actividad física.El propósito de esta investigaciónfue analizar los efectos de la práctica de deporte extraescolar, del agrupamiento deportivo (colectivo o individual) y del sexo en la inteligencia emocional de los adolescentes. La muestra estuvo compuesta por 384 estudiantes de educación secundaria. La edad media de las personas participantes fue de 14.1 años y su distribución por sexos: 53.5% de chicas y 46.5% de chicos. La medida de la inteligencia emocional se llevó a cabo utilizando el Inventario de Inteligencia Emocional de Bar-On en su versión para jóvenes (EQ-I: YV, Bar-On y Parker, 2000). Los resultados mostraron que existe un desarrollo desigual en las diferentes dimensiones de la inteligencia emocional entre el alumnado español de educación secundaria (h2=.478), siendo el estado de ánimo general y la inteligencia interpersonal los rasgos más destacados. Además, se han encontrado diferencias estadísticamente significativas a favor de las chicas en las inteligencias interpersonal (h2=.014) e intrapersonal (h2=.023), superándolas los chicos en la adaptabilidad (h2=.016). Paralelamente se detectó un impacto de la práctica deportiva extraescolar y, en particular, de los deportes colectivos en el estado de ánimo general del alumnado (h2=.028), mientras que la inteligencia intrapersonal está relacionada directamente con la práctica de deportes individuales. Finalmente, se observó un efecto de interacción (h2=.032) entre el agrupamiento deportivo y el sexo que indica que las chicas podrían presentar una ventaja en el desarrollo de su inteligencia intrapersonal mediante la práctica de deportes individuales. (AU)

The development of emotional intelligence has been related in previous studies to sports practice and physical activity. The purpose of this research was to analyze the effects of extracurricular sports practice, sports grouping (collective or individual),and gender on the emotional intelligence of adolescents. The sample comprised 384 secondary school students. Students averaged 14.1 years, being 53.5% girls and 46.5% boys. The measurement of emotional intelligence was carried out using the Bar-On’s Emotional Intelligence Inventory Youth Version (EQ-I: YV, Bar-On and Parker, 2000). Results showed that there is an uneven development in the different dimensions of emotional intelligence among Spanish secondary school students (h2=.478), with general mood andinterpersonal intelligence being the most prominent features. In addition, girls outperformed boys in interpersonal (h2=.014) and intrapersonal intelligences (h2=.023), reaching boys higher scores in adaptability (h2=.016). At the same time, an impact of extracurricular sports practice and, in particular, of team sports on the students’ general state of mind was detected (h2=.028), while intrapersonal intelligence is directly related to the practice of individual sports. Finally, an interaction effect (h2=.032) between sport grouping and sex was observed in intrapersonal intelligence, indicating that girls could present an advantage in the development of this trait when practicing individual sports. (AU)

O desenvolvimento de a inteligência emocional tem sido previamente relacionada com a prática desportiva e com a atividade física. Esta investigação teve como objetivo analisar os efeitos da prática desportiva extracurricular e do agrupamento desportivo (coletivo ou individual) nos tipos de inteligência emocional em adolescentes. A amostra foi composta por 384 estudantes do ensino médio. A idade média dos participantes foi de 14,1 anos e sua distribuição por sexo: 53,5% meninas e 46,5% meninos. O nível de inteligência emocional foi medido através do Inventário de Inteligência Emocional Bar-On, utilizando asua versão para jovens (EQ-I: YV, Bar-On e Parker, 2000). Os resultados sugeriram que há um desenvolvimento desigual nas diferentes dimensões da inteligência emocional nos alunos espanhóis de ensino médio (h2=.478); o humor geral e a inteligência interpessoal foram as características que mais se destacaram. Além disso, foram encontradas diferenças estatisticamente significativas a favor das meninas na inteligência interpessoal (h2=.023)e intrapessoal (h2=.023), superando os meninos na adaptabilidade (h2=.016). Paralelamente, detetou-se um impacto da prática desportiva extracurricular e, em particular, dos desportos coletivos no estado de espírito geral dos alunos (h2=.028), enquanto a inteligência intrapessoal está diretamente relacionada com a prática desportiva individual. Por fim, observou-se um efeito de interação (h2=.032) entre agrupamento desportivo e sexo, indicando que as meninas poderiam ter vantagemno desenvolvimento da sua inteligência intrapessoal através da prática de desportos individuais. (AU)

Menopausal Voice-Related Work Limitation Scale (MenoVWL): Development and Validation.

OBJECTIVES: Menopause has been reported to affect the voice of female professional voice users (FPVUs). The present study aims at the development and validation of a scale to measure self-perceived menopausal voice-related limitation to work in FPVUs, henceforth the Menopausal Voice-Related Work Limitation Scale (MenoVWL). METHODS: Items were drawn from previous studies on impacts of sex steroid hormones on voice, available validated scales, and in-depth interviews with post-menopausal FPVUs. A preliminary version with 16 items was evaluated by a panel of 15 voice experts. The resulting revised version was filled in online, together with questions on current endocrinological reproductive status and related symptoms, history of amenorrhea, professional occupation, and demographic information. Responses concerning only professional voice users were selected and inclusive and exclusive criteria were applied for correct allocation of participants into pre- and post-menopausal stages within a restrict age range;192 responses were subject to factorial analysis for MenoVWL validation. Cronbach's alpha measured internal reliability. The scale was tested by comparing MenoVWL scores between pre- and post-menopausal FPVUs (98 and 94, respectively). RESULTS: Thirteen items were retained from the expert panel evaluation. Items presented a high Content Validity Index (.94 out of 1) and high Item Acceptance Ratio (86.25 %). Both exploratory and confirmatory factorial analysis rendered one dimension scale with an excellent internal consistency (Cronbach's alpha = .9). The results of a Mann-Whitney test showed a higher MenoVWL score for post- as compared to pre-menopausal FPVUs (Z = - 2.818; P = .005). CONCLUSIONS: MenoVWL is a comprehensive and validated scale with a known factor structure. It constitutes a health care and safety outcome self-perceived measure of value to the early detection of voice-related limitations to work in FPVUs during menopause.

What Voice-Related Metrics Change With Menopause? A Systematic Review and Meta-Analysis Study.

Voice complaints associated with menopause have been reported by a substantial number of studies. However, to assess the clinical relevance of menopause to voice is still difficult as the extent to which menopausal symptoms are reflected on voice metrics remains unclear. A comprehensive review and meta-analysis were carried out to identify voice-related metrics that change with menopause and to quantify the magnitude of those changes. Academic Search Premier, Medline, SciELO, Scopus, PubMed, and Web of Science were searched without restriction of publication year until January 2020. Cross-sectional studies comparing voice-related metrics between pre- and post-menopausal women were included. Studies assessing effects of hormonal-replacement therapy were excluded. Datasets with more than one publication were also disregarded. Methodological quality of included studies was assessed applying the Newcastle-Ottawa Scale for cross-sectional studies. Given the heterogeneous nature of the primary studies, random-effects models were applied to pool the estimates. Eight articles were considered eligible for meta-analyses, assessing the effects of menopause on 6 voice metrics: mean fundamental frequency (fo), extracted from (1) speech and (2) from sustained vowel /a/; frequency perturbation measures (3) jitter, (4) shimmer and (5) noise-to-harmonics ratio; and (6) maximum phonation time. Both speech fundamental frequency and fo for sustained vowel /a/ were found to be 0.94 and 1.18 semitones lower in post- as compared to pre-menopausal women, respectively. Although significant, the magnitude of these decreases is below the just noticeable interval difference and well above the cutting point for distinguishing female from male voices. No significant differences were found for jitter, shimmer, noise-to-harmonics ratio, and maximum phonation time. The evaluation of acoustic metrics that reflect a single aspect of voice production at a time may conceal the effects of hormonal shifts during menopause. In addition, several variables interplay during voice production and acoustical measures may constitute weak predictors of vocal folds' status, where changes associated to sex steroid hormones are most likely to occur.

Mechanism of aqueous-phase ozonation of S(IV).

The ozonation of dissolved sulfur dioxide is an important route for sulfate formation, especially in fog and cloud droplets of high pH. However, little is known about the detailed chemical mechanism of this process. We have mapped out the fate of aqueous SO(2) in the presence of ozone by use of density functional theory (DFT) calculations in solution (via the polarized continuum model, PCM), including up to two explicit water molecules. The calculations predict that the hydrolysis of SO(2).H(2)O, although possessing a barrier, is still more energetically favorable than its ozonation. The ozonation of HOSO(2)(-) and SO(3)(2)(-) proceeds without barriers and gives S(VI) products that are more stable than the reagents by 77.1 and 88.6 kcal/mol, respectively. By comparing our calculated pH dependence of the ozonation kinetics to those determined experimentally, we conclude that, despite a high calculated energy barrier to the ozonation of sulfonate (HSO(3)(-)), it is the dominant form of S(IV) in solutions of neutral pH and is the species through which ozonation occurs.

Where does acid hydrolysis take place?

We present the results of computations on the dissociation of HCl and HNO(3) at the air-water interface. Molecular dynamics simulations of the acid molecule and 200 water molecules were propagated for several nanoseconds, and the resulting structures were used as input to QM/MM geometry optimization runs. Approximately 20-30 water molecules were included along with the acid in the QM portion of the calculation, which was carried out at the B3LYP/6-31+G(d) level. Whereas dissociation to ions is always spontaneous in the bulk, we find that acid molecules confined to the water surface dissociate only with the participation of two additional water molecules, forming a "critical cluster" about the solute. Thus acid dissociation may occur in the near-surface zone at a dynamic air-water interface, in agreement with our earlier experimental conclusions [Clifford et al., Phys. Chem. Chem. Phys.. 2007, 9, 1362].

A theoretical investigation of the Co(CO)4--catalyzed carbonylative ring expansion of N-benzoyl-2-methylaziridine to beta-lactams: reaction mechanism and effect of substituent at the aziridine Calpha atom.

The reaction mechanism of the Co(CO)4--catalyzed carbonylative ring expansion of N-benzoyl-2-methylaziridine to afford N-benzoyl-4-methyl-2-azetidinone and N-benzoyl-3-methyl-2-azetidinone was investigated by using the B3LYP density functional theory methodology in conjunction with the conductor polarizable continuum model/united atom Kohm-Sham method to take into account solvent effects. Computations predict that the most favorable reaction mechanism differs from the experimental proposals except for the nucleophilic ring-opening step, which is the rate-determining one. The regioselectivity and stereospecificity experimentally observed is explained in terms of the located reaction mechanism. The substitution of the methyl group at the carbon alpha of aziridine by the phenyl one gives rise to the obtaining of an only product that corresponds to the CO insertion into the C(substituted)-N bond in accordance with experimental findings. When the ethyl group replaces the methyl one the CO insertion occurs into the two C-N bonds, but the regioselectivity of the process is higher than that of the methyl substituent.

A theoretical study of rhodium(I) catalyzed carbonylative ring expansion of aziridines to beta-lactams: crucial activation of the breaking C-N bond by hyperconjugation.

The regioselectivity and enantiospecificity of the [Rh(CO)2Cl]2-catalyzed carbonylative ring expansions of N-tert-butyl-2-phenylaziridine to yield 2-azetidinone and the lack of reactivity of N-tert-butyl-2-methylaziridine along this process were investigated at the B3LYP/6-31G(d) (LANL2DZ for Rh) theory level taking into account solvent effects. According to our results, the regioselectivity in the ring expansion of N-tert-butyl-2-phenylaziridine and the unreactivity of N-tert-butyl-2-methylaziridine experimentally observed are determined by the different degree of activation of the breaking C-N bond in the initial aziridine-Rh(CO)2Cl complex due to its hyperconjugation interaction with the substituent on the carbon atom. When a phenyl substituent is present its hyperconjugation interaction with the C(alpha)-N bond facilitates the insertion of the metal atom into this bond. On the other hand, when the substituent is a methyl group, a larger stability of the initial complex along with a lower stabilization through hyperconjugation of the TS for insertion of the Rh atom into the C(alpha)-N bond make the ring expansion of N-tert-butyl-2-methylaziridine unviable. The enantiospecificity experimentally observed is also reproduced by our calculations given that the stereogenic center is never perturbed to change its configuration.

Radical ring expansion reactions of methylenecyclopropane derivatives: a theoretical study.

The evolution of the primary radicals from 1-(3-bromopropyl)-2-ethyl-3-methylenecyclopropane, 1-(3-bromopropyl)-1-trimethylsilyl-2-methylenecyclopropane, 1-(3-bromobutyl)-2-ethyl-3-methylenecyclopropane, and 1-(3-bromobutyl)-1-trimethylsilyl-2-methylenecyclopropane was theoretically studied at the ROMP2/6-311++G(d,p)//UB3LYP/6-31G(d,p) theory level taking into account the effect of solvent through a PCM-UAHF model. For the propyl-substituted radicals, the attack of the radical center on the double bond takes place most favorably in an exo fashion. The subsequent ring expansions yield the product corresponding to the rupture of the endo C-C bond as the most favorable one in accordance with the experimental results. In the case of 1-(3-bromobutyl)-2-ethyl-3-methylenecyclopropane, the Gibbs energy barriers for the endo and exo attacks are the same, and the subsequent reversible evolution yields the product corresponding to the rupture of the exo C-C bond as the most favorable one through thermodynamic control in agreement with experiment. Finally, for 1-(3-bromobutyl)-1-trimethylsilyl-2-methylenecyclopropane, our calculations predict that the endo attack is 0.8 kcal/mol more favorable than the exo one. In the subsequent reversible ring expansion, the product corresponding to the rupture of the endo C-C bond is kinetically the most favored one in reasonable agreement with the experimental observations.

Relative Gibbs energies in solution through continuum models: effect of the loss of translational degrees of freedom in bimolecular reactions on Gibbs energy barriers.

We present here a cell model for evaluating Gibbs energy barriers corresponding to bimolecular reactions (or processes of larger molecularity) in which a loss of translational degrees of freedom takes place along the reaction coordinate. With this model, we have studied the Walden inversion processes: Xa- + H3CXb --> XaCH3 + Xb- (X = F, Cl, Br, and I). In these processes, our model yields an increase of about 2.3-3.4 kcal/mol in Gibbs energy in solution corresponding to the loss of the translational degrees of freedom when passing from separate reactants to the TS in good agreement with experimental data. The corresponding value in the gas phase is about 6.7-7.1 kcal/mol. When the difference between these two figures is used to correct the results obtained by the standard UAHF implementation of the continuum model, the theoretical results are brought significantly closer to the experimental ones. This seems to indicate that for these reactions the parametrization used does not adequately introduce the increase in Gibbs energy corresponding to the constriction of the translational motion of the species along the reaction coordinate when passing from the gas phase to solution. Therefore, we believe that continuum models could perform much better if we released the parametrization process from the task of taking into account the constriction in translation motion in solution, which could be more adequately evaluated using the cell model proposed here, thus allowing it to focus on better reproducing all the remaining solvation effects.

Three-carbon Dowd-Beckwith ring expansion reaction versus intramolecular 1,5-hydrogen transfer reaction: a theoretical study.

[Reaction: see text]. The evolution of the primary radicals formed by addition of AIBN/HSnBu3 to methyl 1-(3-iodopropyl)-5-oxocyclopentanecarboxylate, methyl (1R,2R)-1-(3-iodopropyl)-2-methyl-5-oxocyclopentanecarboxylate, and methyl (1R,2S)-1-(3-iodopropyl)-2-methyl-5-oxocyclopentanecarboxylate in benzene has been theoretically investigated by ROMP2/6-311++G(2d,2p)//UB3LYP/6-31G(d,p) calculations taking into account the effect of solvent through a PCM-UAHF model. According to the theoretical results, for methyl 1-(3-iodopropyl)-5-oxocyclopentanecarboxylate and methyl (1R,2S)-1-(3-iodopropyl)-2-methyl-5-oxocyclopentanecarboxylate the major product is the cyclooctane derivative from the three-carbon ring expansion, whereas for methyl (1R,2R)-1-(3-iodopropyl)-2-methyl-5-oxocyclopentanecarboxylate the major product is that corresponding to the 1,5-H transposition in agreement with the experimental findings. This different behavior is a consequence of several factors determining the relative energy barriers. The methyl substituent destabilizes the ring expansion process for methyl (1R,2R)-1-(3-iodopropyl)-2-methyl-5-oxocyclopentanecarboxylate because of steric repulsion but favors it in the case of the beta-trans-substituted substrate because it makes possible the evolution of the system along more favorable conformations. The methyl group also favors the 1,5-H transposition rendering the transposed product a tertiary radical. The second stage of the ring expansion process is stabilized by resonance.