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Purpose: To determine if the speed-duration relationship is altered with age and sex of elite Master's runners., Methods: The world's top 10 performances for men and women in three events (800, 1500, and 5000 m) across six age groups (18-34 yr, 40-49 yr, 50-59 yr, 60-69 yr, 70-79 yr, and 80-89 yr) were analyzed from public data to establish theoretical models of the speed-duration relationship. Critical speed (CS) and the curvature constant ( D ') were estimated by fitting the average speeds and performance times with a two-parameter hyperbolic model., Results: Critical speed expressed relative to the 18- to 34-yr-olds, declined with age (92.2% [40-49] to 55.2% [80-89]; P < 0.001), and absolute CS was higher in men than women within each age group ( P < 0.001). The percent difference in CS between the men and women progressively increased across age groups (10.8% [18-34] to 15.5% [80-89]). D ' was lower in women than men in the 60-69 yr, 70-79 yr, and 80-89 yr age groups ( P < 0.001), but did not differ in the 18-34 yr, 40-49 yr, or 50-59 yr age groups., Conclusions: Critical speed progressively decreased with age, likely due to age-related decrements in several physiological systems that cause reduced aerobic capacity. The mechanism for the larger sex difference in CS in the older age groups is unknown but may indicate physiological differences that occur with aging and/or historical sociological factors that have reduced participation opportunities of older female runners resulting in a more limited talent pool., (Copyright © 2022 by the American College of Sports Medicine.)

Baranauskas, Marissa N., Timothy J. Fulton, Alyce D. Fly, Bruce J. Martin, Timothy D. Mickleborough, and Robert F. Chapman. High intraindividual variability in the response of serum erythropoietin to multiple simulated altitude exposures. High Alt Med Biol . 23:85-89, 2022. Purpose: To evaluate within-subject variability in the serum erythropoietin (EPO) response to multiple simulated altitude exposures. Methods: Seven physically active men and women (age 27 ± 3 years, body mass index = 24.6 ± 4.0 kg/m 2 ) were exposed to normobaric hypoxia (fraction of inspired oxygen [F i O 2 ] = 0.14) for 12 hours on three separate occasions. Serum EPO concentrations were measured before exposure (0 hour), after 6 hours, and after 12 hours in hypoxia. The EPO response to hypoxia was calculated as percent change from 0 to 12 hours (ΔEPO 0-12 ). Results: Exposure time had a significant effect on EPO ( p  < 0.001) with concentrations increasing 3.2 ± 1.3 mIU/ml from 0 to 6 hours ( p  = 0.034) and 4.7 ± 1.2 mIU/ml from 0 to 12 hours ( p  = 0.001). Group mean ΔEPO 0-12 remained unchanged ( p  = 0.688) between the three exposures; however, there was considerable intraindividual variability in EPO responses. The intrasubject coefficient of variation for ΔEPO 0-12 was 61% ± 28% (range: 17%-103%) with intrasubject associations ranging r  = 0.052 to r  = 0.651 between repeated exposures. Conclusions: Athletes who routinely supplement training with simulated altitude methods (e.g., hypoxic tents) should expect inconsistent EPO responses to intermittent exposures lasting ≤12 hours.

Purpose: This study aimed to determine if preexisting respiratory muscle fatigue (RMF) alters motoneuronal output, locomotor muscle fatigue, and cycling performance., Methods: Eight trained male cyclists performed 5-km cycling time trials after a resistive breathing task that induced RMF and under control conditions (CON). Motoneuronal output was estimated using vastus lateralis surface electromyography, and locomotor muscle fatigue was quantified as the change in potentiated quadriceps twitch force from preexercise to postexercise., Results: Time to complete the time trial was 1.9% ± 0.9% longer in RMF compared with CON (P < 0.001). Estimated motoneuronal output was lower in RMF compared with CON during 1 km (45% ± 11% vs 53% ± 13%, P = 0.004) and 2 km (45% ± 14% vs 51% ± 14%, P = 0.008), but was not different thereafter. Ventilation was lower in RMF compared with CON during 1 km (114 ± 19 vs 135 ± 24 L·min, P = 0.003) and 2 km (136 ± 23 vs 152 ± 31 L·min, P = 0.009); however, ratings of dyspnea were similar. After the 5-km time trial, locomotor muscle fatigue was attenuated in RMF compared with CON (-22% ± 6%, vs -28% ± 7%, P = 0.02)., Conclusions: Alterations to dyspnea for a given ventilation seem to have constrained power output during cycling exercise, thereby limiting the development of locomotor muscle fatigue. These findings indicate that the respiratory system is an integral component in a global feedback loop that regulates exercise performance and the development of locomotor muscle fatigue.

A catalytic enantioselective approach to the Myrioneuron alkaloids (-)-myrifabral A and (-)-myrifabral B is described. The synthesis was enabled by a palladium-catalyzed enantioselective allylic alkylation, that generates the C(10) all-carbon quaternary center. A key N -acyl iminium ion cyclization forged the cyclohexane fused tricyclic core, while vinyl boronate cross metathesis and oxidation afforded the lactol ring of (-)-myrifabral A. Adaptation of previously reported conditions allowed for the conversion of (-)-myrifabral A to (-)-myrifabral B., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Here we apply microcrystal electron diffraction (MicroED) to the structural determination of transition-metal complexes. We find that the simultaneous use of 300 keV electrons, very low electron doses, and an ultrasensitive camera allows for the collection of data without cryogenic cooling of the stage. This technique reveals the first crystal structures of the classic zirconocene hydride, colloquially known as "Schwartz's reagent", a novel Pd(II) complex not amenable to solution-state NMR or X-ray crystallography, and five other paramagnetic and diamagnetic transition-metal complexes., Competing Interests: The authors declare no competing financial interest., (Copyright © 2019 American Chemical Society.)

The first enantioselective palladium-catalyzed decarboxylative allylic alkylation of fully substituted N -acyl indole-derived enol carbonates forming acyclic all-carbon quaternary stereocenters is reported. Excellent yields up to 99% and enantioselectivities up to 98% ee are obtained through the use of a new electron-deficient phosphinoxazoline (PHOX) ligand. Control of substrate enolate geometry is crucial for high selectivity. The obtained α-quaternary N -acyl indoles are formal ester equivalents, and represent a useful handle for further synthetic transformations.

To determine whether acute exposure to moderate hypoxia alters central and peripheral fatigue and to test whether carbohydrate ingestion impacts fatigue characteristics, 12 trained runners completed three running trials lasting 1 h each at 65% of normoxic maximum oxygen uptake. The first trial was performed in normoxia [inspired O 2 fraction ( F i O 2 ) = 0.21], and the last two trials were completed in hypoxia ( F i O 2  = 0.15). Participants ingested a placebo drink in normoxia (NORM-PLA), a placebo drink in hypoxia (HYP-PLA), or a carbohydrate solution in hypoxia (HYP-CHO). HYP conditions were randomized. Peripheral [change in potentiated quadriceps twitch force (ΔQ tw,pot )] and central [change in voluntary activation (ΔVA)] fatigue were assessed via preexercise-to-postexercise changes in magnetically evoked quadriceps twitch. In HYP, blood was drawn to determine the ratio of free-tryptophan (f-TRP) to branched-chain amino acids (BCAA). After exercise, peripheral fatigue was reduced to a similar degree in normoxia and hypoxia (ΔQ tw,pot  = -4.5 ± 1.3% and -4.0 ± 1.5% in NORM-PLA and HYP-PLA, respectively; P = 0.61). Central fatigue was present after normoxic and hypoxic exercise but to a greater degree in HYP-PLA compared with NORM-PLA (ΔVA: -4.7 ± 0.9% vs. -1.9 ± 0.7%; P < 0.01). Carbohydrate ingestion did not influence central fatigue (ΔVA in HYP-CHO: -5.7 ± 1.2%; P = 0.51 vs. HYP-PLA). After exercise, no differences were observed in the ratio of f-TRP to BCAA between HYP-PLA and HYP-CHO ( P = 0.67). Central fatigue increased during prolonged running exercise in moderate hypoxia although the ratio of f-TRP to BCAA remained unchanged. Ingesting carbohydrates while running in hypoxia did not influence fatigue development. NEW & NOTEWORTHY Hypoxic exposure influences the origin of exercise-induced fatigue and the rate of fatigue development depending on the severity of hypoxia. Our data suggest that moderate hypoxia increases central, but not peripheral, fatigue in trained runners exercising at 65% of normoxic maximum oxygen uptake. The increase in central fatigue was unaffected by carbohydrate intake and occurred although the ratio of free tryptophan to branched-chain amino acids remained unchanged.

Monoorganozinc reagents, readily obtained from alkyl bromides, display excellent reactivity with β,β-disubstituted enones and TMSCl in the presence of Cu(I) and Cu(II) salts to synthesize a variety of cyclic functionalized β-quaternary ketones in 38-99% yields and 9:1-20:1 diastereoselectivities. The conjugate addition features a pronounced improvement in DMA using monoorganozinc bromide reagents. A simple one-pot protocol that harnesses in situ generated monoorganozinc reagents delivers comparable product yields.

In the many scientific endeavors that are driven by organic chemistry, unambiguous identification of small molecules is of paramount importance. Over the past 50 years, NMR and other powerful spectroscopic techniques have been developed to address this challenge. While almost all of these techniques rely on inference of connectivity, the unambiguous determination of a small molecule's structure requires X-ray and/or neutron diffraction studies. In practice, however, X-ray crystallography is rarely applied in routine organic chemistry due to intrinsic limitations of both the analytes and the technique. Here we report the use of the electron cryo-microscopy (cryoEM) method microcrystal electron diffraction (MicroED) to provide routine and unambiguous structural determination of small organic molecules. From simple powders, with minimal sample preparation, we could collect high-quality MicroED data from nanocrystals (∼100 nm, ∼10 -15 g) resulting in atomic resolution (<1 Å) crystal structures in minutes., Competing Interests: The authors declare no competing financial interest.

To determine whether acute exposure to simulated moderate altitude alters locomotor-respiratory coupling (LRC) patterns in runners, 13 trained male distance runners performed a running economy and maximal oxygen uptake (V̇o 2max ) test in normoxia (NORM) and hypoxia (HYP) ([Formula: see text]= 15.8%; ~2,400 m/8,000 ft) on separate days. Running economy (RE), the degree of LRC, stride frequency-to-breathing frequency quotients (SF/f b ), ratings of perceived exertion (RPE), and dyspnea were assessed at three common submaximal speeds and V̇o 2max . SF/f b were significantly lower at each submaximal speed in HYP (12.9 km/h: 2.91 ± 0.20 vs. 2.45 ± 0.17, 14.3 km/h: 2.53 ± 0.17 vs. 2.21 ± 0.14, 16.1 km/h: 2.22 ± 0.14 vs. 1.95 ± 0.09; P < 0.05). The degree of LRC (range: 36-99%) in HYP was not significantly different than NORM at any of the three common submaximal speeds. However, the degree of LRC was significantly higher at V̇o 2max in HYP than NORM (43.8 ± 3.4% vs. 57.1 ± 3.8%; P < 0.05). RE and RPE were similar at all running speeds. Dyspnea was significantly greater in HYP compared with NORM at 16.1 km/h ( P < 0.05). Trained distance runners are able to maintain LRC in HYP, despite increases in breathing frequency. Within this unique population, years of training may enhance and optimize the ability to maintain LRC to minimize metabolic costs and dyspnea. NEW & NOTEWORTHY Exposure to acute altitude causes increases in ventilation at rest and any submaximal exercising workload, which may alter locomotor-respiratory coupling (LRC). Our data suggest that trained distance runners can maintain LRC during acute exposure to simulated moderate altitude, even when breathing frequency is increased at any submaximal pace.