Chemistry of the Au-Thiol Interface through the Lens of Single-Molecule Flicker Noise Measurements.

Chemistry of the Au-S interface at the nanoscale is one of the most complex systems to study, as the nature and strength of the Au-S bond change under different experimental conditions. In this study, using mechanically controlled break junction technique, we probed the conductance and analyzed Flicker noise for several aliphatic and aromatic thiol derivatives and thioethers. We demonstrate that Flicker noise can be used to unambiguously differentiate between stronger chemisorption (Au-SR) and weaker physisorption (Au-SRR') type interactions. The Flicker noise measurements indicate that the gold rearrangement in chemisorbed Au-SR junctions resembles that of the Au rearrangement in pure Au-Au metal contact breaking, which is independent of the molecular backbone structure and the resulting conductance. In contrast, thioethers showed the formation of a weaker physisorbed Au-SRR' type bond, and the Flicker noise measurement indicates the changes in the Au-anchoring group interface but not the Au-Au rearrangement like that in the Au-SR case. Additionally, by employing single-molecular conductance and Flicker noise analysis, we have probed the interfacial electric field-catalyzed ring-opening reaction of cyclic thioether under mild environmental conditions, which otherwise requires harsh chemical conditions for cleavage of the C-S bond. All of our conductance measurements are complemented by NEGF transport calculations. This study illustrates that the single-molecule conductance, together with the Flicker noise measurements can be used to tune and monitor chemical reactions at the single-molecule level.

Achilles tendon dimensions, ankle stiffness and footfall patterns in recreational runners.

The main purpose of this study was to investigate the relationship among Achilles tendon (AT) dimensions, ankle joint stiffness, and footfall patterns in recreational rearfoot and non-rearfoot runners. Based on the foot strike index, a total of 107 runners were divided into rearfoot (47 females/40 males) and non-rearfoot runners (14 females/6 males). All participants had theirs AT dimensions (AT length, AT thickness, and AT moment arm) measured using a combination of ultrasound and motion capture systems. In addition, all performed running trials measured at self-selected speed in laboratory-neutral shoes. A partial correlation coefficient was used for correlations between the selected variables. The results revealed a significant relationship between ankle joint stiffness and level of footfall pattern in rearfoot (r = 0.232, p = 0.032) and non-rearfoot runners (r = -0.811, p < 0.001). The results also suggest a relationship between AT thickness and foot strike index (r = -0.486) in non-rearfoot runners. Runners whose footfall pattern is closer to the heel have greater ankle joint stiffness. Non-rearfoot runners whose footfall pattern is closer to the toe have a thinner AT. Non-rearfoot runners with thicker AT had greater ankle joint stiffness.

A data mining approach for determining biomechanical adaptations in runners who experienced and recovered from patellofemoral pain syndrome.

Patellofemoral pain (PFP) is a common musculoskeletal pain disorder experienced by runners. While biomechanics of those with PFP have been extensively studied, methodological considerations may omit important adaptations exhibited by those experiencing and recovered from pain. Instead of a priori selection of discrete biomechanical variables, a data mining approach was leveraged to account for the high dimensionality of running gait data. Biomechanical data of runners symptomatic for, recovered from, and who had never experienced PFP were collected at the 1st (M1) and 21st (M21) minutes of a treadmill run. Principal component analysis and a logistic regression model were used to classify healthy and symptomatic runners, and a feature ranking process determined the important features. The M1 model achieved an accuracy of 82.76% with features related to knee flexion angle, hip abduction moment and gluteus maximus activation, while the M21 model required an additional nine features to achieve an accuracy of 79.31%. Data for recovered runners were projected onto the models, resulting in five and seven out of twelve symptomatic classifications at M1 and M21, respectively. Following the onset of pain, a greater number of features were required to classify runners with PFP, suggesting they may experience individual pain adaptation strategies.

Does lateral banking and radius affect well-trained sprinters and team-sports players during bend sprinting?

This study investigated the short-term responses of step characteristics in sprinters and team-sports players under different bend conditions. Eight participants from each group completed 80 m sprints in four conditions: banked and flat, in lanes two and four (L2B, L4B, L2F, L4F). Groups showed similar changes in step velocity (SV) across conditions and limbs. However, sprinters produced significantly shorter ground contact times (GCT) than team sports players in L2B and L4B for both left (0.123 s vs 0.145 s and 0.123 s vs 0.140 s) and right steps (0.115 s vs 0.136 s and 0.120 s vs 0.141 s) (p > 0.001-0.029; ES = 1.15-1.37). Across both groups, SV was generally lower in flat conditions compared to banked (Left: 7.21 m/s vs 6.82 m/s and Right: 7.31 m/s vs 7.09 m/s in lane two), occurring due to reduced step length (SL) rather than step frequency (SF), suggesting that banking improves SV via increased SL. Sprinters produced significantly shorter GCT in banked conditions that led to non-significant increases in SF and SV, highlighting the importance of bend sprinting specific conditioning and training environments representative of indoor competition for sprint athletes.

Achilles tendon structure is associated with regular running volume and biomechanics.

Achilles tendinopathy was reported to have the highest incidence proportion of all running-related injuries. The purpose of this study was to analyse the association between the Achilles tendon structure and running activity status. 350 healthy participants (runners and inactive controls, 30-50 years) participated in this research. Each participant completed questionnaires: socioeconomic, psychological, physical activity habits, running status and history and VISA-A. Magnetic resonance imaging, anthropological, running biomechanics and 14 days of physical activity monitoring assessments were performed. There was a higher odd of being in the upper quartile of the Achilles tendon T2* relaxation time with higher maximal knee extension moment independent of age and sex. Compared with runners who ran 21-40 km per week, non-runners and those who ran more than 40 km per week had increased odds of having longest the Achilles tendon T2* relaxation time. Regular running of 21 to 40 km per week is related to the Achilles tendon T2* relaxation time indicating possibly better water content and collagen orientation in these runners with compare to inactive non-runners or highly active individuals. In addition, Achilles tendon T2* relaxation time as indirect indicator of the Achilles tendon structure was positively related to the maximal knee extension moment during running.

Trusting our machines: validating machine learning models for single-molecule transport experiments.

In this tutorial review, we will describe crucial aspects related to the application of machine learning to help users avoid the most common pitfalls. The examples we present will be based on data from the field of molecular electronics, specifically single-molecule electron transport experiments, but the concepts and problems we explore will be sufficiently general for application in other fields with similar data. In the first part of the tutorial review, we will introduce the field of single-molecule transport, and provide an overview of the most common machine learning algorithms employed. In the second part of the tutorial review, we will show, through examples grounded in single-molecule transport, that the promises of machine learning can only be fulfilled by careful application. We will end the tutorial review with a discussion of where we, as a field, could go from here.

Running-Related Achilles Tendon Injury: A Prospective Biomechanical Study in Recreational Runners.

There are relatively few running studies that have attempted to prospectively identify biomechanical risk factors associated with Achilles tendon (AT) injuries. Therefore, the aim was to prospectively determine potential running biomechanical risk factors associated with the development of AT injuries in recreational, healthy runners. At study entry, 108 participants completed a set of questionnaires. They underwent an analysis of their running biomechanics at self-selected running speed. The incidence of AT running-related injuries (RRI) was assessed after 1-year using a weekly questionnaire standardized for RRI. Potential biomechanical risk factors for the development of AT RRI injury were identified using multivariable logistic regression. Of the 103 participants, 25% of the sample (15 males and 11 females) reported an AT RRI on the right lower limb during the 1-year evaluation period. A more flexed knee at initial contact (odds ratio = 1.146, P = .034) and at the midstance phase (odds ratio = 1.143, P = .037) were significant predictors for developing AT RRI. The results suggested that a 1-degree increase in knee flexion at initial contact and midstance was associated with a 15% increase in the risk of an AT RRI, thus causing a limitation of training or a stoppage of running in runners.

Head control and head-trunk coordination as a function of anticipation in sidestepping.

Head reorientation precedes body reorientation during direction change to facilitate gaze realignment, thus enhancing perceptual awareness. Whole body kinematics are dependent on the available planning time. The purpose of this study was to assess the role of anticipation on head control and head-trunk coordination during sidestepping tasks. Fourteen male collegiate athletes performed anticipated and unanticipated sidestepping tasks. Transverse plane head, trunk and heading direction, as well as head-trunk coordination were assessed. During change of direction tasks, we observed greater head orientation towards the new travel direction, followed by heading direction and then trunk direction during both anticipated and unanticipated tasks. With reduced planning time, heading in the preparatory phase and trunk rotation in the preparatory and stance phases were significantly less oriented towards the new travel direction, with no differences in head rotation. During anticipated sidestepping, significantly greater in-phase coordination was observed during the preparatory phase compared to unanticipated sidestepping. Head reorientation facilitates gaze realignment and may be prioritized irrespective of planning time during sidestepping tasks. During anticipated trials, the head and trunk move more synchronously compared to unanticipated sidestepping, highlighting the potential benefits of aligning the degrees of freedom earlier in the change of direction stride and optimizing perceptual awareness.

Age differences in running biomechanics during footstrike between preschool children and adults.

This study aimed to compare impact loading between two age groups of preschool children (3-4 and 5-6 years old) and one group of young adults representing mature level of running skill (n = 15 per group). Three-dimensional biomechanical data were collected during running barefoot, in minimalist and running shoes. A two-way mixed ANOVA was performed to assess age and footwear differences in vertical instantaneous loading rate (VILR). An interaction was found in VILR. Older (5-6) preschoolers had 30-31% lower VILR than younger (3-4) (p = 0.012, d = 1.02; p = 0.001, d = 1.18) and adults had 51-77% lower VILR than younger preschoolers (p = 0.001, d = 1.85; p = 0.001, d = 2.82) in minimalist and running shoes, respectively. Additionally, adults had lower VILR than older preschoolers in running shoes (p = 0.001, d = 2.68). No differences were found between older children and adults in barefoot and minimalist shoes. Loading decreased with increasing age, particularly in minimalist and running shoes. Unchanged cadence and running speed did not explain the decrease of VILR during preschool age. The explanation likely underlies in lower limb alignment during footstrike and developmental ontogenetic changes.

Surface Stiffness and Footwear Affect the Loading Stimulus for Lower Extremity Muscles When Running.

ABSTRACT: Willwacher, S, Fischer, KM, Rohr, E, Trudeau, MB, Hamill, J, and Brüggemann, G-P. Surface stiffness and footwear affect the loading stimulus for lower extremity muscles when running. J Strength Cond Res 36(1): 82-89, 2022-Running in minimal footwear or barefoot can improve foot muscle strength. Muscles spanning the foot and ankle joints have the potential to improve performance and to reduce overuse injury risk. Surface stiffness or footwear use could modify the intensity of training stimuli acting on lower extremity joints during running. The purpose of this study was to systematically investigate external ankle, knee, and hip joint moments during shod and barefoot running while considering the stiffness of the running surface. Two footwear conditions (barefoot and neutral running shoe) and 4 surface conditions (Tartan, Tartan + Ethylene Vinyl Acetate [EVA] foam, Tartan + artificial turf, Tartan + EVA foam + artificial turf) were tested at 3.5 m·s-1. Repeated measures analysis of variance revealed that barefoot running in general and running barefoot on harder surfaces increased and decreased ankle (between +5 and +26%) and knee (between 0 and -11%) joint moments, respectively. Averaged over all surfaces, running barefoot was characterized by a 6.8° more plantarflexed foot strike pattern compared with running shod. Foot strike patterns were more plantarflexed on harder surfaces; the effects, however, were less than 3°. Most surface effects were stronger in barefoot compared with shod running. Surface stiffness may be used to modulate the loading intensity of lower extremity muscles (in particular extrinsic and intrinsic foot muscles) during running. These results need to be considered when coaches advise barefoot running as a method to improve the strength of extrinsic and intrinsic foot muscles or when trying to reduce knee joint loading.

Marker Placement Reliability and Objectivity for Biomechanical Cohort Study: Healthy Aging in Industrial Environment (HAIE-Program 4).

In large cohort studies, due to the time-consuming nature of the measurement of movement biomechanics, more than one evaluator needs to be involved. This may increase the potential occurrence of error due to inaccurate positioning of markers to the anatomical locations. The purpose of this study was to determine the reliability and objectivity of lower limb segments length by multiple evaluators in a large cohort study concerning healthy aging in an industrial environment. A total of eight evaluators performed marker placements on five participants on three different days. Evaluators placed markers bilaterally on specific anatomical locations of the pelvis, thigh, shank and foot. On the right foot, markers were placed in anatomical locations to define a multi-segmental foot model. The position of the marker at the anatomical locations was recorded by a motion capture system. The reliability and objectivity of lower limb segment lengths was determined by the intraclass correlation coefficient of a two-way random model and of the two-way mixed model, respectively. For all evaluators for all segments, the average reliability and objectivity was greater than 0.8, except for the metatarsus segment (0.683). Based on these results, we can conclude that multiple evaluators can be engaged in a large cohort study in the placement of anatomical markers.

Comparing Leg Quasi-Stiffness Methods Across Running Velocities.

This study investigated the differences between 5 commonly used methods to calculate leg stiffness over a range of running velocities. Thirteen male, habitually rearfoot, recreational runners ran on a force instrumented treadmill for a 5-minute running session. Each session consisted of 30-second intervals at 6 progressively faster speeds from 2.5 m·s-1 through 5.0 m·s-1 with each interval speed increasing by 0.5 m·s-1. Two-way within-factors repeated-measures analyses of variance were used to evaluate leg stiffness and length. A one-way repeated-measures analysis of variance was used to evaluate the slope of each trend line of each model across speeds. Pearson correlations were used to compare the relationship between the different computational methods. The results indicated that the direct stiffness methods increased with speed whereas the indirect stiffness methods did not. The direct methods were strongly correlated with each other as were the indirect methods. However, there were no strong correlations between the direct and indirect methods. These differences can be mostly attributed to how each individual stiffness method calculated leg length. It is important for researchers to understand these differences when conducting future studies and comparing past studies.

Stable Coordination Variability in Overground Walking and Running at Preferred and Fixed Speeds.

Coordination variability (CV) is commonly analyzed to understand dynamical qualities of human locomotion. The purpose of this study was to develop guidelines for the number of trials required to inform the calculation of a stable mean lower limb CV during overground locomotion. Three-dimensional lower limb kinematics were captured for 10 recreational runners performing 20 trials each of preferred and fixed speed walking and running. Stance phase CV was calculated for 9 segment and joint couplings using a modified vector coding technique. The number of trials required to achieve a CV mean within 10% of 20 strides average was determined for each coupling and individual. The statistical outputs of mode (walking vs running) and speed (preferred vs fixed) were compared when informed by differing numbers of trials. A minimum of 11 trials were required for stable mean stance phase CV. With fewer than 11 trials, CV was underestimated and led to an oversight of significant differences between mode and speed. Future overground locomotion CV research in healthy populations using a vector coding approach should use 11 trials as a standard minimum. Researchers should be aware of the notable consequences of an insufficient number of trials for overall study findings.

Scale-Up of Room-Temperature Constructive Quantum Interference from Single Molecules to Self-Assembled Molecular-Electronic Films.

The realization of self-assembled molecular-electronic films, whose room-temperature transport properties are controlled by quantum interference (QI), is an essential step in the scale-up of QI effects from single molecules to parallel arrays of molecules. Recently, the effect of destructive QI (DQI) on the electrical conductance of self-assembled monolayers (SAMs) has been investigated. Here, through a combined experimental and theoretical investigation, we demonstrate chemical control of different forms of constructive QI (CQI) in cross-plane transport through SAMs and assess its influence on cross-plane thermoelectricity in SAMs. It is known that the electrical conductance of single molecules can be controlled in a deterministic manner, by chemically varying their connectivity to external electrodes. Here, by employing synthetic methodologies to vary the connectivity of terminal anchor groups around aromatic anthracene cores, and by forming SAMs of the resulting molecules, we clearly demonstrate that this signature of CQI can be translated into SAM-on-gold molecular films. We show that the conductance of vertical molecular junctions formed from anthracene-based molecules with two different connectivities differ by a factor of approximately 16, in agreement with theoretical predictions for their conductance ratio based on CQI effects within the core. We also demonstrate that for molecules with thioether anchor groups, the Seebeck coefficient of such films is connectivity dependent and with an appropriate choice of connectivity can be boosted by ∼50%. This demonstration of QI and its influence on thermoelectricity in SAMs represents a critical step toward functional ultra-thin-film devices for future thermoelectric and molecular-scale electronics applications.

Tibial stress during running following a repeated calf-raise protocol.

Tibial stress fractures are a problematic injury among runners. Increased loading of the tibia has been observed following prolonged weight-bearing activity and is suggested to be the result of reduced activity of the plantar flexor muscles. The musculature that spans the tibia contributes to bending of the bone and influences the magnitude of stress on the tibia during running. Participant-specific models of the tibia can be used as a non-invasive estimate of tibial stress. This study aimed to quantify tibial stress during running using participant-specific bone geometry and to compare tibial stress before and after a protocol of repeated muscular contractions of the plantar flexor muscle group. Fourteen participants who run recreationally were included in the final analysis of the study. Synchronized force and kinematic data were collected during overground running before and after an exhaustive, weighted calf-raise protocol. Bending moments and stress at the distal third of the tibia were estimated using beam theory combined with inverse dynamics and musculoskeletal modeling. Bone geometry was obtained from magnetic resonance images. There was no difference in stress at the anterior, posterior, medial, or lateral peripheries of the tibia after the calf-raise protocol compared with before. These findings suggest that an exhaustive, repeated calf-raise protocol did not alter tibial stress during running.

Does footwear affect articular cartilage volume change after a prolonged run?

The aim of this study was to investigate knee intra-articular cartilage volume changes after a prolonged running bout in three footwear conditions. Twelve participants performed 75-minute running bouts in the three footwear conditions. Before and after each running bout, magnetic resonance imaging (MRI) scans were obtained using a high-resolution 3.0 Tesla MRI. Three-dimensional reconstruction of the cartilage plates of the patella, the femur, and the tibia was created to quantify cartilage volume change due to the 75-minute running bout. Three-dimensional biomechanical data were also collected using an integrated motion capture and force treadmill system. There were no statistically significant differences among shoe conditions for all anatomical regions. However, significant cartilage volume reductions at all anatomical sites were observed after the 75-minute running bout in each footwear condition. These data suggest that the intra-articular knee cartilage undergoes a significant reduction in cartilage volume during a prolonged run that may indicate an increase in joint loading. There was a considerable variation in cartilage volume between participants across footwear conditions indicating an individual cartilage volume response to footwear. An individualistic approach to footwear recommendations may help in minimizing this change in cartilage.

Associated ACL risk factors differences during an unanticipated volleyball blocking movement.

The lateral tilt of the arms accompanied by trunk lateral tilt is a typical blocking manoeuvre in volleyball. However, during this unanticipated blocking movement, an associated risk of ACL injury may result. The aim of the present study was to compare associative ACL risk factors at the initial contact and the first and second peak of VGRF during an unanticipated blocking movement with different arm positions. Synchronized kinematic and kinetic data were collected for each trial of each condition. Student paired t-tests and effect size were used to determine differences between two conditions (S - with arms straight up from the body) and (T - with the arms and trunk laterally tilted). The results showed that the T condition significantly decreases knee flexion, increases VGRF at the foot contact, first peak force and increases the valgus moment at the first peak force. The values of the associated risk factors for a non-contact ACL injury appear to be related to the tilted arm position accompanied by trunk tilt towards to right lower limb during landing. The players should be taught to land with greater knee flexion and, if possible, a double-leg landing to decrease right lower limb loading during the blocking manoeuvre.

Reliability of a measurement technique for achilles tendon length.

Recently, there has been an increasing amount of literature dealing with new methods of Achilles tendon (AT) length measurement. However, most of these studies measured the AT length between the calcaneus and medial head of the gastrocnemius and the reliability of such a measurement has not been satisfactorily presented. The purpose of this study was to determine the reliability of the measurement of AT length within and between sessions. AT length was measured by using a combination of ultrasound imaging and optoelectronic stereophotogrammetry. Nineteen healthy athletes visited the lab on six different days where the AT length was measured on both lower extremities: 1) from the calcaneus to the mid-point of the medial and lateral heads of the gastrocnemius; and 2) from the calcaneus to the soleus musculotendinous attachment. The reliability results indicated high intraclass correlation coefficients (ICC > 0.8), a low typical error (< 0.6) and a standard error of measurement (SEM < 5.5 mm) for all measured AT lengths on within and between sessions. This non-invasive reliable measurement method may be recommended for sport science research purposes.

Whole-body control of anticipated and unanticipated sidestep manoeuvres in female and male team sport athletes.

The purpose of this study was to investigate the influence of sex and planning time on spatial and temporal aspects of the whole-body centre of mass (CoM) mechanics during sidestepping performance. Seventeen female and 17 male collegiate team sport athletes completed seven anticipated and seven unanticipated sidestep trials during which three-dimensional CoM data were recorded. Female athletes had a reduced ability to reorient their CoM towards the desired direction of travel (lower medio-lateral and anterior-posterior CoM velocity) than their male counterparts, with reduced medial (closer to stance foot) and increased posterior positioning of CoM relative to the stance foot (p < 0.05). When planning time was limited, female and male athletes performed sidestepping with CoM further from the stance foot (more medial) and more anterior than in the anticipated condition (p < 0.05) at reduced medio-lateral velocities. Sex and condition control strategy differences were evident both in the preparatory phase and the stance phase. The current research draws attention to the foreseen benefits of training athletes, with particular emphasis on females, to direct CoM towards the desired direction of travel in the preparatory and stance phases within temporally constrained situations for improved performance.

Using a Support-Vector Machine Algorithm to Classify Lower Extremity EMG Signals During Running Shod/Unshod With Different Foot Strike Patterns.

The present study aimed to use a Support Vector Machine (SVM) algorithm to identify and classify shod and barefoot running as well as rearfoot and forefoot landings. Ten habitually shod runners ran at self-selected speed. Thigh and leg muscle surface electromyography (EMG) were recorded. Discrete Wavelet transformation (DWT) and Fast Fourier transformation (FFT) were used for the assembly of vectors for training and classification of a SVM. Using the FFT coefficients for the gastrocnemius and tibialis anterior muscles presented the best results for differentiating between rearfoot/forefoot running in the window before foot-floor contact possibly due to these muscles' critical role in determining which part of the foot will first touch the floor. The classification rate was 76% and 67% respectively, with a probability of being random of 0.5% and 4% respectively. For the same terms and conditions of classification, the DWT produced a reduction in the percentage of correctness of 60% and 53% with a probability of having reached these levels randomly of 15% and 35%. In conclusion, based on EMG signals, the use a FFT to train a SVM was a better option to differentiate running forefoot/rearfoot than to use the DWT. Shod/barefoot running could not be differentiated.