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Background: The aim was to analyze changes in normal functional parameters of gait analysis by aging, sex, and body mass index (BMI). Methods: A cross-sectional study with a consecutive sample of asymptomatic subjects was performed between 2014 and 2020. Primary outcomes were time and force parameters (contact time and center of force [CoF] time), in the heel, midfoot, and metatarsal areas, measured using an in-office force platform. Results: A total of 156 subjects (312 feet) were included, including 67% of women with a mean age of 47 years. The mean of total contact time was similar in males and females (P = .695) and across BMI (P = .413). Contact time did not show differences by region (P = .648 heel, P = .286 midfoot, and P = .690 metatarsal). CoF time in the heel and metatarsal areas did not change between males and females (P = .288 and P = .879, respectively); meanwhile, it was different in midfoot (P = .002). Maximum force showed a reduction between sexes in the heel (P = .039) but did not in the midfoot and metatarsal areas. By age, differences were detected in the heel and metatarsal areas in females (P = .002 and P = .001) and the metatarsal area in males (P = .001). According to the age groups, total contact time increased in females (P = .001) but not in males (P = .018), and no differences were detected between foot areas. In females, CoF time did not change either foot areas or age groups. In males, CoF time values increased in the midfoot area in the older group (P = .001). Conclusion: Time variables did not change by foot region, independent of age, sex, and BMI. Heel maximum force decreased in females, probably linked to adaptive phenomena by aging. The midfoot remains stable, and acts as an undamaged "bridge." These parameters could be interpreted as normal in asymptomatic subjects. Level of Evidence: Level III, diagnostic and prognostic.

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The C-X bond cleavage in different methyl halides (CH3X; X = Cl, Br, I) mediated by 5,6-dimethylbenzimidazole-bis(dimethylglyoximate)cobalt(II) (CoIICbx) was theoretically investigated in the present work. An SN2-like mechanism was considered to simulate the chemical process where the cobalt atom acts as the nucleophile and the halogen as the leaving group. The reaction path was computed by means of the intrinsic reaction coordinate method and analyzed in detail through the reaction force formalism, the quantum theory of atoms in molecules (QTAIM), and the calculation of one-electron density derived quantities, such as the source function (SF) and the spin density. A thorough comparison of the results with those obtained in the same reaction occurring in presence of 5,6-dimethylbenzimidazole-bis(dimethylglyoximate)cobalt(I) (CoICbx) was conducted to reveal the main differences between the two cases. The reactions mediated by CoIICbx were observed to be endothermic and possess higher activation energies in contrast to the reactions where the CoICbx complex is present. The latter was supported by the reaction force results, which suggest a relationship between the activation energy and the ionization potentials of the different nucleophiles present in the cleavage reaction. Moreover, the SF results indicates that the lower axial ligand (i.e., 5,6-dimethylbenzimidazole) exclusively participates on the first stage of the reaction mediated by the CoIICbx complex, while for the CoICbx case, it appears to have an important role along the whole process. Finally, the QTAIM charge analysis indicates that oxidation of the cobalt atom occurs in both cases; at the same time, it suggests the formation of an uncommon two-center one-electron bond in the CoIICbx case. The latter was confirmed by means of electron localization calculations, which resulted in a larger electron count at the Co-C interatomic region for the CoICbx case upon comparison with its CoIICbx counterpart.

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SUMMARY: As it is currently played, volleyball is a game in which success depends in large measure on the athleticism of the participants. The aim of this research was to point out the importance of the cycle of stretching and shortening in different jumps for elite volleyball players. Thus, it is common for volleyball athletes to place considerable emphasis on jump training. Not surprisingly, overload injuries of the knee and ankle joints, both acute and chronic, occur frequently among volleyball players and are related to the volume of jump training and skill repetition. Understanding the biomechanics of jumping is therefore a prerequisite for designing effective training programs which minimize the risk of overuse injuries that may result from excessive jumping, and the repetitive mechanical loading of muscles and joints that are involved in jump training Muscles acting about a joint function naturally through a combination of eccentric (lengthening) and concentric (shortening) activations. In the lower limb, the stretch-shortening cycle is a reflex arc in which the tendomuscular system acting about the knee or ankle is eccentrically preloaded (stretched) in the loading or impact phase of the jump before concentrically shortening in the push-off or take-off phase.

RESUMEN: Actualmente, el voleibol es un juego en el que el éxito depende en gran medida del atletismo de los participantes. El objetivo de esta investigación fue señalar la importancia del ciclo de estiramiento y acortamiento en diferentes saltos para jugadores de voleibol de élite. Es común que los atletas de voleibol pongan un énfasis considerable en el entrenamiento de salto. No es sorprendente que las lesiones por sobrecarga de las articulaciones de la rodilla y el tobillo, tanto agudas como crónicas, ocurran con frecuencia entre los jugadores de voleibol y estén relacionadas con el volumen de entrenamiento de saltos y la repetición de destrezas. Comprender la biomecánica del salto es, por lo tanto, un requisito previo para diseñar programas de entrenamiento efectivos que minimicen el riesgo de lesiones por uso excesivo que pueden resultar de un salto excesivo y la carga mecánica repetitiva de los músculos y las articulaciones que están involucrados en el entrenamiento del salto. Los músculos que actúan sobre una articulación funcionan de forma natural a través de una combinación de activaciones excéntricas (alargamiento) y concéntricas (acortamiento). En el miembro inferior, el ciclo de estiramiento-acortamiento es un arco reflejo en el que el sistema tendomuscular que actúa sobre la rodilla o el tobillo se precarga (estira) excéntricamente en la fase de carga o impacto del salto antes de acortarse concéntricamente en el despegue o toma. -fase de apagado.

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The analysis of the reaction force and its topology has provided a wide range of fruitful concepts in the theory of chemical reactivity over the years, allowing to identify chemically relevant regions along a reaction profile. The reaction force (RF), a projection of the Hellmann-Feynman forces acting on the nuclei of a molecular system onto a suitable reaction coordinate, is partitioned using the interacting quantum atoms approach (IQA). The exact IQA molecular energy decomposition is now shown to open a unique window to identify and quantify the chemical entities that drive or retard a chemical reaction. The RF/IQA coupling offers an extraordinarily detailed view of the type and number of elementary processes that take reactants into products, as tested on two sets of simple reactions.

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In this study, the degradation mechanism of chloroacetanilide herbicides in the presence of four different nucleophiles, namely: Br-, I-, HS-, and S2O3-2, was theoretically evaluated using the dispersion-corrected hybrid functional wB97XD and the DGDZVP as a basis set. The comparison of computed activation energies with experimental data shows an excellent correlation (R2 = 0.98 for alachlor and 0.97 for propachlor). The results suggest that the best nucleophiles are those where a sulfur atom performs the nucleophilic attack, whereas the other species are less reactive. Furthermore, it was observed that the different R groups of chloroacetanilide herbicides have a negligible effect on the activation energy of the process. Further insights into the mechanism show that geometrical changes and electronic rearrangements contribute 60% and 40% of the activation energy, respectively. A deeper analysis of the reaction coordinate was conducted, employing the evolution chemical potential, hardness, and electrophilicity index, as well as the electronic flux. The charge analysis shows that the electron density of chlorine increases as the nucleophilic attack occurs. Finally, NBO analysis indicates that the nucleophilic substitution in chloroacetanilides is an asynchronous process with a late transition state for all models except for the case of the iodide attack, which occurs through an early transition state in the reaction.

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Perception of external loads may be a central topic to understand adjustments to the mechanical demands during movement. Nevertheless, the association between the perceived and the real load received is still controversial. This study aimed to correlate vertical ground reaction force (vGRF) to the perception of impact in different regimens of stimulus application. Ten physically active men performed drop jumps from four different heights (0.20, 0.40, 0.60 and 0.80 m). A force plate measured the vGRF, while perception of impact was evaluated through Borg's Ratings of Perceived Exertion. Higher values of maximum vGRF (Fy_max) and impulse of the first 50 ms (I_50), and reduced time to reach Fy_max indicate increased external forces as drop jump height raised. Perception of impact increased gradually with increasing jump height for I_50. Fy_max and I_50 showed moderate to strong correlations to perceived load for 70% and 90% of participants, respectively. Higher and different intensity of stimulus facilitated the perception of impact, presenting moderate to strong correlations to kinetic parameters related to external load during landing from drop jump. Perception of higher impacts could be used as a surrogate to monitor 'real' impacts and possibly also for managing impact-related injury risk.

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OBJECTIVES: To evaluate the clinical characteristics, ground reaction force (GRF), and function of the plantar muscles and dorsiflexors of the ankle in runners with and without Achilles tendinopathy (AT) and in non-runners. METHODS: Seventy-two participants (42 men, 30 women; mean age: 37.3±9.9 years) were enrolled in this cross-sectional study and divided into three groups: AT group (ATG, n=24), healthy runners' group (HRG, n=24), and non-runners' group (NRG, n=24). Both ankles were evaluated in each group. The American Orthopedic Foot and Ankle Society (AOFAS) Ankle-Hindfoot Scale was used for clinical and functional evaluation. GRF was evaluated using force plates and muscle strength was evaluated using an isokinetic dynamometer. RESULTS: The AOFAS scores were lower in the ATG. The strike impulse was higher in the ATG than in the HRG and NRG. However, GRF was similar among the groups. The ATG exhibited lower total work at 120°/s speed than the HRG. The peak torque in concentric dorsiflexion was lower in the NRG than in the ATG and HRG. The peak torque and total work in concentric plantar flexion were lower in the NRG than in the ATG. The peak torque and total work in eccentric plantar flexion were lower in the NRG than in the ATG and HRG. CONCLUSION: Runners with AT showed higher strike impulse, lower muscle strength of the plantar flexors, and higher clinical and functional damage.

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Quantum chemical calculations were used to study the mechanism of Diels-Alder reactions involving chiral anthracenes as dienes and a series of dienophiles. The reaction force analysis was employed to obtain a detailed scrutiny of the reaction mechanisms, it has been found that thermodynamics and kinetics of the reactions are quite consistent: the lower the activation energy, the lower the reaction energy, thus following the Bell-Evans-Polanyi principle. It has been found that activation energies are mostly due to structural rearrangements that in most cases represented more than 70% of the activation energy. Electronic activity mostly due to changes in σ and π bonding were revealed by the reaction electronic flux (REF), this property helps identify whether changes on σ or π bonding drive the reaction. Additionally, new global indexes describing the behavior of the electronic activity were introduced and then used to classify the reactions in terms of the spontaneity of their electronic activity. Local natural bond order electronic population analysis was used to check consistency with global REF through the characterization of specific changes in the electronic density that might be responsible for the activity already detected by the REF. Results show that reactions involving acetoxy lactones are driven by spontaneous electronic activity coming from bond forming/strengthening processes; in the case of maleic anhydrides and maleimides it appears that both spontaneous and non-spontaneous electronic activity are quite active in driving the reactions.

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BACKGROUND: Down Syndrome (DS) is a genetic condition presenting delay in acquisition of main motor milestones, such as walking. Although studies have been investigating the biomechanical parameters during land walking performed by individual with DS, the literature is scarce regarding kinetic parameters analysis in this population, specially during water walking. RESEARCH QUESTION: This study sought to assess the vertical ground reaction force (Fz) of walking performed in water and on land at different speeds by individuals with DS. METHODS: Fourteen adults with DS (age: 27.9 ± 7.9 years; body mass: 58.4 ± 12.9 kg; height: 1.4 ± 0.1 m, body mass index: 29.2 ± 5.4 kg.m-2) completed two sessions of data collection, one on land and another in aquatic environment. The protocol consisted of walking performed at three self-selected speeds (slow, comfortable and fast) in randomized order. The Fz was assessed with a waterproof force plate in each condition. Two-way repeated-measures ANOVA (environment and speed), with Bonferroni's post hoc tests, were used for analysis. A significance level was set as α = 0.05. RESULTS: Significant differences were observed between environments (p < 0.001), with reduced first peak of Fz (68-73%), second peak of Fz (66-70%), loading rate (75-78%) and impulse (40-41%) in the water walking for all speeds analyzed. In the aquatic environment, no significant difference was observed for the first and second Fz peaks with the increasing speed of walking. Moreover, the loading rate significantly increased (p = 0.019) as the impulse significantly reduced (p < 0.001) in the higher speeds. SIGNIFICANCE: Individuals with DS present reduced Fz outcomes during water walking in comparison to land. Therefore, water walking may be performed by individuals with DS with safe vertical loads on lower limbs regardless the self-selected speed for rehabilitation, correction of gait and training purposes.

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The chemical reactivity of the first- and second-generation Grubbs catalysts has always been a significant issue in olefin metathesis. In the present work, we study the [2+2] cycloreversion/cycloaddition and the alkylidene rotation involved into the interconversion of the ruthenacyclobutane intermediate, through the reaction force and reaction force constant analysis. It has been found that the structural contribution controls the barrier energy in the interconversion of ruthenacyclobutane via [2+2] cycloreversion/cycloaddition, which is slightly lower in the second generation of Grubbs catalysts while its electronic contribution is slightly higher, which unveils a major rigidity and donor/acceptor properties of the NHC. This finding explains a greater structural contribution in the rate constant. Moreover, on the basis of the reaction force constant, the process can be classified as "two-stage"-concerted reactions, noting a more asynchronous process when the first generation is used as a catalyst.Finally, a similar analysis into the alkylidene rotation was performed. It was determined that [2+2] cycloreversion and alkylidene rotations take place in a sequential manner, the energy barrier is again controlled by structural reorganization, and the pathway is less asynchronous.