Effect of maturity status on force-velocity relationships in a ballistic lower limb test in high-level soccer players.

This study aimed to investigate the effect of maturity status on force-velocity relationships in a ballistic lower limb (BLL) test in high-level soccer adolescents and young adults. The population was 61 adolescents (13.0-17.9 years) and 23 young adults (18.0-26.2 years). Subjects completed the BLL test on a ballistic ergometer equipped with two force plates and a linear encoder. Following Samozino's method, maximal power output (Pmax), force (F0) and velocity (v0) were determined. An allometric model was applied to Pmax and F0 with body mass (BM) and fat-free mass (FFM). Significant effects of maturity status were found for absolute Pmax, F0, relative Pmax to BM and FFM, relative F0 to FFM and F0 allometrically scaled to BM and FFM (p = 0.02 to p < 0.001; η = 0.10 to η = 0.49). There was no significant effect for Pmax allometrically scaled to BM and FFM, F0 relative to BM and v0. Body dimensions explain group differences in Pmax whereas for F0, qualitative factors explain the differences between the groups. As maturity status and body dimensions influence Pmax, these factors should be considered when assessing explosive short efforts. This could help to better identify potential athletic talent and adapt training content.

ArgTX-636, a polyamine isolated from spider venom: A novel class of melanogenesis inhibitors.

To discover new molecules with an inhibitory activity of melanogenesis a hundred of scorpions, snakes, spiders and amphibians venoms were screened for their capacity to inhibit mushroom tyrosinase using 3,4-l-dihydroxyphenylalanine (l-DOPA) as substrate. The Argiope lobata spider venom proved to be the most active. HPLC fraction containing Argiotoxine-636 (ArgTX-636), a polyamine known for its numerous biological activities, was found to also show a good regulation activity of melanogenesis by inhibiting DOPA and 5,6-dihydroxyindole-2-carboxylic acid (DHICA) oxidases activities, wore by tyrosinase (TYR) and tyrosinase-related protein 1 (TRP-1), respectively. Our results demonstrate that ArgTX-636 reduced the mushroom tyrosinase activity in a dose-dependent way with a maximal half inhibitory concentration (IC50) value of 8.34µM, when l-DOPA is used as substrate. The Lineweaver-Burk study showed that ArgTX-636 is a mixed type inhibitor of the diphenolase activity. Moreover, ArgTX-636 inhibits DHICA oxydase activity of mushroom tyrosinase activity with IC50 at 41.3µM. ArgTX-636 has no cytotoxicity in B16F10 melanoma cells at concentrations up to 42.1µM. The effect of ArgTX-636 on melanogenesis showed that melanin production in B16F10 melanoma cell decreased by approximatively 70% compared to untreated cells. ArgTX-636 displayed no significant effect on the TYR expression while the protein level of TRP-1 decreased in B16F10 cells. Thus, ArgTX-636 could have particular interest for cosmetic and/or pharmaceutical use in order to reduce important dermatoses in black and mixed skins.

Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries.

Electrochemical energy storage is one of the main societal challenges of this century. The performances of classical lithium-ion technology based on liquid electrolytes have made great advances in the past two decades, but the intrinsic instability of liquid electrolytes results in safety issues. Solid polymer electrolytes would be a perfect solution to those safety issues, miniaturization and enhancement of energy density. However, as in liquids, the fraction of charge carried by lithium ions is small (<20%), limiting the power performances. Solid polymer electrolytes operate at 80 °C, resulting in poor mechanical properties and a limited electrochemical stability window. Here we describe a multifunctional single-ion polymer electrolyte based on polyanionic block copolymers comprising polystyrene segments. It overcomes most of the above limitations, with a lithium-ion transport number close to unity, excellent mechanical properties and an electrochemical stability window spanning 5 V versus Li(+)/Li. A prototype battery using this polyelectrolyte outperforms a conventional battery based on a polymer electrolyte.

Mechanism involved of post-exercise cold water immersion: Blood redistribution and increase in energy expenditure during rewarming.

Thermogenesis is well understood, but the relationships between cold water immersion (CWI), the post-CWI rewarming and the associated physiological changes are not. This study investigated muscle and systemic oxygenation, cardiorespiratory and hemodynamic responses, and gastrointestinal temperature during and after CWI. 21 healthy men completed randomly 2 protocols. Both protocols consisted of a 48 minutes heating cycling exercise followed by 3 recovery periods (R1-R3), but they differed in R2. R1 lasted 20 minutes in a passive semi-seated position on a physiotherapy table at ambient room temperature. Depending on the protocol, R2 lasted 15 minutes at either ambient condition (R2_AMB) or in a CWI condition at 10°C up to the iliac crest (R2_CWI). R3 lasted 40 minutes at AMB while favoring rewarming after R2_CWI. This was followed by 10 minutes of cycling. Compared to R2_AMB, R2_CWI ended at higher V ˙ O2 in the non-immersed body part due to thermogenesis (7.16(2.15) vs. 4.83(1.62) ml.min-1.kg-1) and lower femoral artery blood flow (475(165) vs. 704(257) ml.min-1) (p < 0.001). Only after CWI, R3 showed a progressive decrease in vastus and gastrocnemius medialis O2 saturation, significant after 34 minutes (p < 0.001). As blood flow did not differ from the AMB protocol, this indicated local thermogenesis in the immersed part of the body. After CWI, a lower gastrointestinal temperature on resumption of cycling compared to AMB (36.31(0.45) vs. 37.30(0.49) °C, p < 0.001) indicated incomplete muscle thermogenesis. In conclusion, the rewarming period after CWI was non-linear and metabolically costly. Immersion and rewarming should be considered as a continuum rather than separate events.

Towards a more individualised assessment of post-training fatigue in young footballers.

Despite improvements in training load and fatigue monitoring, fatigue status may adversely affect intrinsic risk factors, particularly in young footballers. This study aimed to better individualise the fatigue effects of a 75-min football training session in young elite male players. Eighteen players (15.6 ± 1.7 years) completed a test battery before and after a football training session. Assessments included capillary blood samples (HCO3 -, lactate, pH), subjective ratings of muscle soreness and fatigue. Functional tests included 30 m field sprint, laboratory drop jump (DJ) and horizontal force-velocity (H-FvP). The k-means method was applied to the first two dimensions of principal component analysis of changes in the H-FvP and DJ tests. Football training resulted in significant physiological changes and functional impairments, in particular an increase in interlimb asymmetry in the DJ test. No significant fatigue effect was found on the H-FvP test data. However, confirming the interest of combining the two tests, cluster analysis revealed two subgroups: In the H-FvP test, Cluster 1 decreased in V ‾ 0 (p < 0.001) and P ‾ max (p < 0.01), while Cluster 2 decreased in F ‾ 0 (p < 0.001). In the DJ test, Cluster 1 decreased in mean velocity (p < 0.01), relative mean and maximum power (p < 0.01) during push-off, while Cluster 2 decreased in relative mean push-off force (p < 0.01) and increased in interlimb asymmetry during braking (p < 0.01). This study highlights the contribution and complementarity of the H-FvP and DJ tests to improve individual screening for fatigue-related functional changes in footballers. Extrapolated values from the H-FvP test led to the identification of two subgroups with opposite fatigue profiles. One subgroup showed increased interlimb asymmetry in DJ, indicating an increased risk of injury with fatigue. These findings highlight the need for individualised fatigue assessment in young footballers.

Immobilization of styrene-substituted 1,3,4-oxadiazoles into thermoreversible luminescent organogels and their unexpected photocatalyzed rearrangement.

A series of styrene-substituted 1,3,4-oxadiazoles has been designed and investigated as new low-molecular-weight organogelators. The photophysical properties of the resulting thermoreversible organogels have been characterized by UV/Vis absorption and luminescence spectroscopies. Surprisingly, the gelation ability of the oxadiazoles depended on the presence of the styrene moiety as gelation of the investigated oxadiazoles did not take place in its absence. Gel formation was accompanied by a modification of the fluorescence of the organogelators in the supramolecular state. UV irradiation of the gels caused a rearrangement of the immobilized 1,3,4-oxadiazoles bearing a styrene moiety by a tandem [4+2] and [3+2] cascade reaction. Structure modification and color change of the gels were also evident upon irradiation.

Kinetic subtleties of nitroxide mediated polymerization.

Due to the academic and industrial interest of Nitroxide Mediated Polymerization (NMP), a lot of investigations have focused on the kinetics of this process. During the last decade, although the simplified kinetic scheme--equilibrium reactions between dormant species (alkoxyamine) and active species (alkyl radicals and nitroxides), propagation reaction of the macro-alkyl radical, and termination reactions--was suitable to predict the main trends at the macromolecular level, it has become obvious that it was not sufficient to describe all the kinetic effects involved in the NMP process. Indeed, like the conventional radical polymerization, NMP should be described as a 3 stage process including initiation, propagation, and self- and cross-termination. These two types of radical polymerization differ by the occurrence during NMP of an activation/deactivation process involving the dormant species in both the initiation and propagation stages. Evidence is provided of the importance of the rate of homolysis of the initiator (alkoxyamines) and of the rate of the first alkyl radical addition onto the monomer for the success of NMP. Thus, the fundamental kinetics of the main reactions involved in NMP as well as side-reactions are also discussed in this tutorial review.

Dynamic interactive membranes with pressure-driven tunable porosity and self-healing ability.

When pressure is applied to dynamic interactive membranes consisting of micelles composed of a triblock copolymer, their morphologies can be fine-tuned. Membranes with a range of porosities are accessible which can regulate and thereby control filtration performance and also display effective autonomous healing.

Structural effects on the photodissociation of alkoxyamines.

The search for photosensitive alkoxyamines represents a huge challenge. The key parameters governing the cleavage process remain unknown. The dissociation process of light sensitive alkoxyamines is studied as a function of their chemical structures. The photochemical properties of 6 selected compounds are investigated by ESR and laser flash photolysis. It is found that (i) the selectivity of the cleavable N-O vs. C-O bond and (ii) the efficiency of the nitroxide formation are strongly related to the alkoxyamine structure. The distance between the chromophore and the aminoxy group is a key parameter for an efficient pathway of the radical generation as displayed by the photopolymerization ability of these alkoxyamines.

Scorpio single radius total knee arthroplasty. A minimal five-year follow-up multicentric study.

PURPOSE: Our goal was to evaluate the five-year follow-up results of the Scorpio single radius total knee arthroplasty. METHOD: We performed a retrospective study based upon a multicentre database to evaluate the minimum five-year follow-up clinical and radiological results of 747 patients (831 knees) who underwent primary Scorpio single radius total knee arthroplasty. RESULTS: The mean age of the patients was 71.9 years. At a minimal five-year follow-up, 141 patients were lost to follow-up, 83 patients had died, eight patients had undergone revision of a component, and the remaining 589 patients (602 knees) had a complete clinical and radiological evaluation after a median of six years (range, 5-8). The mean clinical component of the knee score was 92.2 points, and the mean functional component of the knee score was 76.9 points. At last follow-up, 530 of the 602 knees were rated as excellent or good. Only four knees developed patellar complications requiring revision. The survival rate at six years was 95.2% ± 1.9% and 98.3% ± 0.6 with revision for any reason and revision for mechanical failure as the end point, respectively. CONCLUSION: This medium-term study indicates favourable clinical and radiological results for this single flexion-extension radius design arthroplasty, with a low complication rate on the patellar side.

Physiological and Mechanical Indices Serving the New Cross-Country Olympic Mountain Bike Performance.

OBJECTIVES: To identify relevant physiological, mechanical, and strength indices to improve the evaluation of elite mountain bike riders competing in the current Cross-Country Olympic (XCO) format. METHODS: Considering the evolution of the XCO race format over the last decade, the present testing protocol adopted a battery of complementary laboratory cycling tests: a maximal aerobic consumption, a force-velocity test, and a multi-short-sprint test. A group of 33 elite-level XCO riders completed the entire testing protocol and at least 5 international competitions. RESULTS: Very large correlations were found between the XCO performance and maximal aerobic power output (r = .78; P < .05), power at the second ventilation threshold (r = .83; P < .05), maximal pedaling force (r = .77; P < .05), and maximum power in the sixth sprint (r = .87; P < .05) of the multi-short-sprint test. A multiple regression model revealed that the normalized XCO performance was predicted at 89.2% (F3,29 = 89.507; r = .95; P < .001) by maximum power in the sixth sprint (ß = 0.602; P < .001), maximal pedaling rate (ß = 0.309; P < .001), and relative maximal aerobic power output (ß = 0.329; P < .001). DISCUSSION: Confirming our expectations, the current XCO performance was highly correlated with a series of physiological and mechanical parameters reflecting the high level of acyclic and intermittent solicitation of both aerobic and anaerobic metabolic pathways and the required qualities of maximal force and velocity. CONCLUSION: The combination of physiological, mechanical, and strength characteristics may thus improve the prediction of elite XCO cyclists' performance. It seems of interest to evaluate the ability to repeatedly produce brief intensive efforts with short active recovery periods.

Photodissociation rate constants of new light sensitive alkoxyamines.

The photochemical properties of two new photocleavable alkoxyamines bearing a benzophenone-derived chromophore were studied by electron spin resonance (ESR). The CO bond cleavage has been demonstrated and the photolysis rate constants (k(d) ) determined over a large range of light intensity through the monitoring of the nitroxide concentration in aerated conditions. The obtained kinetic data highlight for the first time the linear dependence of k(d) on the light intensity for alkoxyamines: this should be a driving factor for nitroxide mediated radical photopolymerization (NMP(2) ).

Importance of the position of the chromophore group on the dissociation process of light sensitive alkoxyamines.

New photosensitive alkoxyamines have been designed using molecular orbital calculations to improve the selective CO versus NO cleavage. The targeted light-sensitive alkoxyamine is synthesized in one step and its reactivity under UV has been investigated using both ESR and LFP. The ability of this alkoxyamine to control the photopolymerization of n-butyl acrylate is evidenced through a process called nitroxide-mediated photopolymerization NMP(2) . The selected alkoxyamine is finally used to prepare covalently bonded multilayered micropatterns. This original application highlights the high potential of this technique for some specific applications that require spatial control.

Online sonification improves cycling performance through kinematic and muscular reorganisations.

Based on a previous study that demonstrated the beneficial effects of sonification on cycling performance, this study investigated which kinematic and muscular activities were changed to pedal effectively. An online error-based sonification strategy was developed, such that, when negative torque was applied to the pedal, a squeak sound was produced in real-time in the corresponding headphone. Participants completed four 6-min cycling trials with resistance values associated with their first ventilatory threshold. Different auditory display conditions were used for each trial (Silent, Right, Left, Stereo), where sonification was only presented for 20 s at the start of minutes 1, 2, 3, and 4. Joint kinematics and right leg muscular activities of 10 muscles were simultaneously recorded. Our results showed participants were more effective at pedalling when presented sonification, which was consistent with previously reported findings. In comparison to the Silent condition, sonification significantly limited ankle and knee joint ranges of motion and reduced muscular activations. These findings suggest performance-based sonification significantly affected participants to reduce the complexity of the task by altering the coordination of the degrees of freedom. By making these significant changes to their patterns, participants improved their cycling performance despite lowering joint ranges of motion and muscular activations.

Robust supramolecular network on Ag(111): hydrogen-bond enhancement through partial alcohol dehydrogenation.

Alcohol oxidation and self-assembly: the in situ oxidation of hydroxyl functional groups to quinone groups promotes the formation of enhanced hydrogen bonds and allows reorganization of the resulting supramolecular self-assemblies, which evolve from a weakly bound dense phase to a strongly bound nanoporous open structure (see picture).

Convenient access to biocompatible block copolymers from SG1-based aliphatic polyester macro-alkoxyamines.

SG1-based poly(d,l-lactide) (PLA) or poly(epsilon-caprolactone) (PCL) macro-alkoxyamines were synthesized and further used as macroinitiators for nitroxide-mediated polymerization (NMP) of 2-hydroxyethyl (meth)acrylate (HE(M)A) to obtain the corresponding PLA- or PCL-PHE(M)A block copolymers. First, a PLA-SG1 macro-alkoxyamine was prepared by 1,2-intermolecular radical addition (IRA) of the MAMA-SG1 (BlocBuilder) alkoxyamine onto acrylate end-capped PLA previously prepared by ring-opening polymerization. The NMP of HEA monomer from the PLA-SG1 macro-alkoxyamine appeared to be well controlled in the presence of free SG1 nitroxide, contrary to that of HEMA. In the latter case, adjustable molecular weights could be obtained by varying the HEMA to macro-alkoxyamine ratio. The versatility of our approach was then further applied to the preparation of PHEMA-b-PCL-b-PHEMA copolymers from a alpha,omega-di-SG1 functionalized PCL macro-alkoxyamine previously obtained from a PCL diacrylate by IRA. Preliminary studies of neuroblast cultures on these PCL-based copolymer films showed acceptable cyto-compatibility, demonstrating their potential for nerve repair applications.

Organized formation of 2D extended covalent organic frameworks at surfaces.

The development of nanoscale masking for particle deposition is exceedingly important to push the future of nanoelectronics beyond the current limits of lithography. We present the first example of ordered hexagonal covalent nanoporous structures deposited in extended arrays of near monolayer coverage across a Ag(111) surface. The networks were formed from the deposition of the reagents from a heated molybdenum crucible between 370 and 460 K under ultrahigh vacuum (UHV) onto a cleaned Ag(111) substrate and imaged using a scanning tunneling microscope (STM). Two surface covalent organic frameworks (SCOFs) are presented; the first is formed from the deposition of 1,4-benzenediboronic acid (BDBA) and its dehydration to form the boroxine-linked SCOF-1, the second is formed from the co-deposition of BDBA and 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) to form a dioxaborole-linked SCOF-2 network. The networks were found to produce nanoporous structures of 15 A for SCOF-1 and 29 A for SCOF-2, which agreed with theoretical pore sizes determined from DFT calculations. Both SCOFs were found to have exceptional thermal stability, maintaining their structure until approximately 750 K, which was found to be the polymer degradation temperature from thermal gravimetric analysis (TGA).

Effect of the carboxylate salt on the C--ON bond homolysis of SG1-based alkoxyamines.

Alkoxyamines and persistent nitroxides are important regulators of the nitroxide mediated radical polymerization (NMP). Since the polymerization time decreases with increasing values of the homolysis rate constant (kd) for the C--ON bond between the polymer chain and the nitroxide moiety, the factors influencing kd are of considerable interest. Environmentally friendly polymerization methods, such as NMP in emulsion medium, have now been developed. The success of the polymerization depends not only on the strength of the C--ON bond but also on the solubility of the initiator/controller alkoxyamines, which control the nucleation. Various salts of SG1-based alkoxyamines (S+-OOCCMeH-SG1) labelled 1 a-f, where S+=Li+ (a), Na+ (b), K+ (c), nBu3HN+ (d), NH4+ (e), and nBu4N+ (f) are prepared, all of which are soluble in most organic solvents (e.g. pentane, dichlomethane, benzene, ethanol, etc.) as well as in water. Their kd values, which are measured in tert-butylbenzene, reveal unexpected behaviors depending on the diastereoisomers. For the RR/SS diatereoisomers (i.e. slowly homolyzing isomers), kd was not found to be sensitive to any of the salts, whereas for the RS/SR diastereoisomers (i.e. quickly homolyzing isomers), kd is observed to decrease to a greater or lesser extent depending on the type of salt. The conformations of the diastereoisomers of several salts are determined by means of DFT calculations, and the orbital interactions are studied by natural bond orbital (NBO) analysis.

Understanding the Physiological Requirements of the Mountain Bike Cross-Country Olympic Race Format.

Objectives: To evaluate the physiological requirements imposed by the current mountain biking Cross-Country Olympic (XCO) format. Methods: Sixteen Cross-Country cyclists competing at national or international level participated in this study. All participants completed a simulated and a real official race on a cycling-accredited race track. Oxygen consumption (O2) and heart rate (HR) values expressed as %O2max and %HRmax, respectively, were divided into three physiological intensity zones. The first zone (Z1) was the physiological region below VT1, the second zone (Z2) corresponded to a region between VT1 and VT2, and the third zone (Z3) was located between VT2 and VO2max. For power output, an additional fourth zone was considered above maximal aerobic power (MAP). Results: When competing in the current XCO format, 37.0 ± 17.9% of the race is performed above the second ventilatory threshold at a mean intensity of 87% O2max and 25% of the race was spent above MAP. This contribution varied between laps, with a very high intensity during the first lap and more aerobic subsequent laps. The durations of most of the periods beyond MAP oscillated between 5 and 30 s. Between these short, repeated bursts, low-intensity periods of exercise were recorded. Conclusion: The current XCO race format is an acyclical and intermittent exercise comparable to high-intensity team sports. Moreover, our results highlight the relevance of O2 values when analyzing XCO performance, they should be combined with commonly used HR and/or power output data.

Liquid chromatography at the critical conditions in pure eluent: an efficient tool for the characterization of functional polystyrenes.

Functional polymers are usually separated by liquid chromatography at critical conditions (LC-CC) using a desorli/adsorli mixture as eluent. In this paper, we describe LC-CC using dimethylformamide (DMF) as pure eluent at 72 degrees C and its application to the analysis of functional polystyrenes. The critical adsorption point is reached by tuning the temperature so that the lack of repeatability is no longer a problem. We analysed several batches of polystyrenes, exhibiting different molecular weights and functionalities. We were able to differentiate di-, mono- and non-functional polystyrenes, bearing carboxylic acid, hydroxyl or nitroxide moieties. The behaviour of these polystyrenes expressed by the experimental results was compared with their behaviour described by the LC-CC theory through the calculation of the effective interaction parameter of each end group. The technique also makes it possible to quantify the fractions of different functional polymers in a blend.