Conformational Switching of A Nano-Size Urea-bridged Zn(II)Porphyrin Dimer by External Stimuli.

For the first time, explicit stabilization of all the three conformers, viz. (cis,cis), (cis,trans) and (trans,trans), of a 'nano-sized' highly-flexible urea-bridged Zn(II)porphyrin dimer have been achieved via careful manipulations of external stimuli such as solvent dielectrics, temperature, anionic interactions, axial ligation and surface-induced stabilization. The conformers differ widely in their structures, chemical and photophysical properties and thus have vast potential applicability. X-ray structural characterizations have been reported for the (cis,cis) and (cis,trans)-conformers. While (cis,cis) conformer stabilized exclusively in dichloromethane, more polar solvents resulted in the stabilization of (cis,trans) and (trans,trans)-conformers. Low temperature promotes the stabilization of (cis,trans)-conformer while rise in temperature facilitates flipping to the (cis,cis) one. Significantly, exclusive stabilization of the (trans,trans)-isomer has been illustrated using acetate anion which facilitates H-bonding with the two amide linkages of the urea spacer. Remarkably, HOPG surface facilitates stabilization of the energetically challenging (trans,trans)-conformer via CH···p and p···p interactions with the solid surface to the porphyrinic cores. DFT calculations demonstrate that the relative stability of the conformers can be modulated upon slight external perturbations as also observed in the experiment. Several factors contributing towards the conformational landscape for the highly flexible urea-bridged porphyrin dimers have been mapped.

The feasibility of using an auditory cue to elicit anticipatory postural adjustments for a posterior perturbation.

When humans are exposed to a predictable external perturbation, they usually generate anticipatory postural adjustments (APAs), which reduce the effect of potential body disturbance. However, when an external perturbation comes from behind and as such unpredicted, no APAs are generated, which challenges postural control. The aim of this study was to examine whether humans exposed to unpredictable perturbations could generate APAs using an auditory cue. Ten young adults were exposed to external perturbations hitting their shoulders from behind with or without an auditory cue prior to the physical impact. Electromyography (EMG) activities of eight trunk and leg muscles and center-of-pressure (COP) displacements were recorded and analyzed during the anticipatory and compensatory phases of postural control. Outcome measures included the latencies and integrals of muscle activities, COP displacements, and indices of co-contraction and reciprocal activation of muscles. The results showed that young adults were able to rely on an auditory cue to generate APAs prior to external perturbations coming from behind, and they demonstrated stronger APAs with training. Moreover, they utilized co-contraction of ventral and dorsal muscles as their APA response. The outcome provides a foundation for future studies aiming at using auditory cues to facilitate the generation of APAs and improve postural control in people with impaired balance while exposed to perturbations.

Older adults can rely on an auditory cue to generate anticipatory postural adjustments prior to an external perturbation.

To minimize the potential postural disturbance induced by predictable external perturbations, humans generate anticipatory postural adjustments (APAs) using visual information about a perturbation. However, it is unknown whether older adults can generate APAs relying on auditory information. Ten older adults received external perturbations (a) with visual information but no auditory information available, (b) without neither visual nor auditory information, (c) with both visual and auditory information available, and (d) participated in training with only auditory information available. In addition, they were tested again after 1 week of washout period. Electromyography activities of eight leg and trunk muscles and ground reaction forces were recorded and analyzed during the anticipatory and compensatory phases. Outcome measures included the latencies and integrals of muscle activities, and center-of-pressure displacements. After a short period of training, participants were able to rely on the auditory cue only to generate APAs close to that when the visual information was available. In addition, after 1 week of washout period, they were able to partially retain the skill to rely on auditory cues to generate APAs. The outcome provides a foundation for future studies focusing on utilizing auditory cues to optimize postural control in individuals who have balance or vision deficit.

Vibratory cue training elicits anticipatory postural responses to an external perturbation.

Anticipatory postural adjustments (APAs) represent the feedforward mechanism of neuromuscular control essential for maintaining balance under predictable perturbations. The importance of vision as a distal sensory modality in the generation of APAs is well established. However, the capabilities of external cues in generating APAs are less explored. In the present study, vibratory cue was investigated for its reliability among healthy individuals in generating anticipatory response under external perturbation in the absence of vision. Ten participants, in quiet stance, were provided with external perturbation in the form of pendulum impact in anterior-posterior (AP) direction under conditions of: both vision and vibratory cue absent; vision present but vibratory cue was absent; vision and vibratory cue both were present; only vibratory cue is present with vision being absent. EMG activities of the leg muscles and displacement of center of pressure (COP) in AP direction were recorded. The data were later analyzed and quantified in the time frame of anticipatory and compensatory phases. The results showed that with training, participants were able to generate significant APAs relying on the vibratory cue alone. Improvement in APAs was accompanied by minimizing the need for larger CPA and improved stability (COP displacement) under perturbation. The study outcome indicates the possibility of using vibratory cues for APA-based interventions.

The role of an auditory cue in generating anticipatory postural adjustments in response to an external perturbation.

Anticipatory postural adjustments (APAs) are usually generated to minimize the potential postural disturbance induced by predictable external perturbations. Visual information about a perturbation is important for the generation of APAs, but whether people can rely on auditory information to generate APAs is unknown. The aim of this study was to investigate the role of an auditory cue in generating APAs when visual information is not available. Fifteen young adults participated in the study. They received external perturbations a) with visual information but no auditory information available, b) without neither visual nor auditory information, c) with both visual and auditory information available, and d) with only auditory information available. Electromyography (EMG) activities of eight leg and trunk muscles and displacements of the center-of-pressure (COP) were recorded and analyzed during the anticipatory and compensatory (CPAs) phases. Outcome measures included the latencies and integrals of muscle activities, COP displacements, and indices of co-contraction and reciprocal activation of muscles. The results showed that after a short training, participants were able to rely only on the auditory cue to generate APAs comparable to that when the visual information was available. In addition, a training effect was found such that the participants demonstrated stronger APAs and less demands for CPAs through the training trials. The outcome provides a foundation for future studies focusing on the utilization of auditory cues for postural control in older adults and individuals who have vision deficit.

Do perturbation-evoked responses result in higher reaction time costs depending on the direction and magnitude of perturbation?

To date, little work has focused on whether cognitive-task interference during postural response execution is influenced by the direction and/or magnitude of the perturbation applied. Hypothetically, the increased difficulty associated with a backward loss of balance could necessitate increased allocation of cognitive resources to counteract destabilizing forces. The current study investigated these relationships using a paradigm in which individuals performed a cognitive task (auditory Stroop task during quiet stance; baseline condition). In certain trials, a translation of the support surface was concurrently evoked (magnitude: small or large; direction: forward or backward) which required a postural response to maintain balance. Ten healthy young adults completed four blocks of these experimental trials (26 randomized trials/block). Postural stability during balance recovery was evaluated using the margin of stability (MoS), while Stroop task performance was based on reaction time cost (RTC) and differences between experimental conditions. Results showed no effect of perturbation direction on RTC, but there was an observed MoS increase at peak extrapolated center of mass excursion following a small perturbation evoked concurrently with the cognitive task. No effect of cognitive-task performance was detected for MoS during stepping strategies (followed large perturbations). Instead, increased RTC were observed relative to the fixed base of support responses. In general, young adults adopted a "posture-first" strategy, regardless of perturbation direction, reinforcing the importance of cognition in the maintenance of upright balance.

Anticipatory postural adjustments associated with a loading perturbation in children with hemiplegic and diplegic cerebral palsy.

Anticipatory postural adjustments (APAs) in preparation for predictable externally induced loading perturbation were studied in children with typically development (TD), hemiplegic (HEMI), and diplegic (DIPL) cerebral palsy. Twenty-seven children (n = 9 in each group) were asked to stand and catch a load dropped from a pre-specified height. Electrical activity of the leg and trunk muscles and center of pressure (COP) displacements were recorded to quantify the APAs. All groups were able to generate APAs prior to the perturbation, but the magnitude was smaller and the onset was delayed in the dorsal (agonist) postural muscles in both HEMI and DIPL as compared to TD. HEMI and DIPL also generated APAs in the antagonist postural muscles. Anticipatory backward COP displacement was significantly different from the baseline value only in the TD and HEMI. HEMI and DIPL displayed a different postural control strategy; HEMI showed no difference in background postural activity from TD, but with diminished APAs in the agonist postural muscles compared to TD, while DIPL showed a higher background postural activity and diminished APAs in the agonist postural muscles compared to TD. These differences are important to consider when designing rehabilitation programs to improve posture and movement control in children with hemiplegic and diplegic cerebral palsy.

Multimodal training protocols on unstable rather than stable surfaces better improve dynamic balance ability in older adults.

BACKGROUND: There has been growing interest in using unstable devices in training protocols. This study aimed to assess the effectiveness of two multimodal exercise interventions (i.e., on stable and unstable surfaces) on dynamic balance control and lower limb strength in older adults. METHODS: Sixty-two older adults were randomly assigned to two intervention groups (N = 20, stable group; N = 19, unstable group), and to a control group (N = 18). In this single-blinded randomized controlled study, the two intervention groups underwent a 12-week training program twice a week for 45 min, consisting of strength and balance exercises. The stable (ST) group performed the training program over stable surfaces, while the unstable (UNST) group over unstable surfaces. Dynamic balance was assessed by computing the center of pressure (CoP) trajectory while a driven movable platform induced an unexpected perturbation of the base of support. Specifically, we considered the following CoP-related parameters within a 2.5-s temporal window from the beginning of the perturbation: displacement (Area95), mean velocity (Unit Path), anterior-posterior first peak (FP), post perturbation variability (PPV), and maximal oscillations (ΔCoPMax). The dominant quadriceps strength was measured through an isometric maximal voluntary contraction on an instrumented chair. RESULTS: Four out of five CoP-related parameters (i.e., Area95, Unit Path, ΔCoPMax, and PPV) significantly improved in the UNST group from a minimum of 14.28% (d = 0.44) to a maximum of 52.82% (d = 0.58). The ST group significantly improved only in two (i.e., ΔCoPMax, and PPV) out of five CoP-related parameters with an enhancement of 12.48% (d = 0.68) and 19.10% (d = 1.06). Both intervention groups increased the maximal isometric quadriceps strength (UNST:17.27%, d = 0.69; ST:22.29%, d = 0.98). The control group did not show changes in any of the parameters considered. CONCLUSIONS: Stable surfaces promoted faster increments of muscular strength. Unstable surfaces were more effective in enhancing dynamic balance efficiency. These findings suggested the employment of multimodal training on unstable rather than stable surfaces to potentially lower the incidence of falls in older adults. TRIAL REGISTRATION: NCT05769361, retrospectively registered 13 March 2023, https://clinicaltrials.gov/study/NCT05769361?lat=45.3661864&lng=11.8209139&locStr=Padova,%20Italy&distance=50&page=11&rank=107 .

Effect of suspensory strategy on balance recovery after lateral perturbation.

Postural stability is essential for performing daily activities and preventing falls, whereby suspensory strategy with knee flexion may play a role in postural control. However, the contribution of the suspensory strategy for postural control during sudden lateral perturbation remains unclear. We aimed to determine how suspensory strategy contributed to postural adjustment during sudden perturbation in the lateral direction and what knee flexion setting maximized its effect. Eighteen healthy young adults (10 male and 8 female) participated in this study. Kinematic data during lateral perturbation at three velocities (7, 15, and 20 cm/s) were collected under three knee flexion angle conditions (0°, 15°, and 65°) using motion capture technology. Postural adjustments to the external perturbation were assessed by four parameters related to the temporal aspects of the center of mass (COM): reaction time, peak displacement/time and reversal time, and minimum value of the margin of stability (minimum-MOS). Our results showed that the COM height before the perturbation significantly lowered with increasing knee flexion angle. The COM reaction times for low and mid perturbation velocities were delayed at 65° of knee flexion compared to 0° and 15°, and the COM reversal times were significantly shorter at 65° of knee flexion than at 0° and 15° across all perturbation velocities. The minimum-MOS at the high-velocity of perturbation was significantly smaller at 65° of knee flexion than at 0° and 15°. In conclusion, the adoption of a suspensory strategy with slight knee flexion induced enhanced stability during sudden external and lateral perturbations. However, excessive knee flexion induced instability.

Investigation of adaptive muscle synergy modulated motor responses to grasping perturbations.

This study investigated how muscle synergies adapt in response to unexpected changes in object weight during lifting tasks. The aim was to discover which motor control strategies individuals use to maintain their grasping performance. Muscle synergies were extracted from the muscle activity of fifteen healthy participants who lifted objects of identical appearance but varying weights in a randomized order, which introduced artificial perturbations. Reaching and manipulation phases of object lifting were analyzed using constrained non-negative matrix factorization and k-means clustering. Participants exhibited a perturbation-independent and thus consistent recruitment of spatial synergy components, while significant adaptations in muscle synergy activation occurred in response to unexpected perturbations. Perturbations caused by unexpectedly heavy objects led to delayed and gradual increases in muscle synergy activation until the force required to lift the object was reached. In contrast, perturbations caused by lighter objects led to reductions in excess muscle synergy activation occurring later. Sensorimotor control maintains the modularity of muscle synergies. Even when external mechanical perturbations occur, the grasping performance is preserved, and control is adapted solely through muscle synergy activation. These results suggest that using pure spatial synergy components as control signals for myoelectric arm prostheses may prevent them from malfunctioning due to external perturbations.

Perturbation-Based Balance Exercise Using a Wearable Device to Improve Reactive Postural Control.

Reactive postural control is an important component of the balance function for fall prevention. Perturbation-based balance exercises improve reactive postural control; however, these exercises require large, complex instruments and expert medical guidance. This study investigates the effects of unexpected perturbation-based balance exercises using a wearable balance exercise device (WBED) on reactive postural control. Eighteen healthy adult males participated in this study. Participants were assigned to the WBED and Sham groups. In the intervention session, participants in the WBED group randomly underwent unexpected perturbation in the mediolateral direction, while the Sham group performed the same exercises without perturbation. Before and after the intervention session, all participants underwent evaluation of reactive balance function using air cylinders. Peak displacement (D), time at peak displacement (T), peak velocity (V), and root mean square (RMS) of center of pressure (COP) data were measured. For mediolateral and anteroposterior COP (COPML and COP[Formula: see text]), the main effects of group and time factors (pre/post) were investigated through the analysis of variance for split-plot factorial design. In the WBED group, the D-COPML and V-COPML of the post-test significantly decreased compared to those of the pre-test (p = 0.017 and p = 0.003, respectively). Furthermore, the D-COPAP and RMSAP of the post-test significantly decreased compared to those of the pre-test (p = 0.036 and p = 0.015, respectively). This study proved that the perturbation-based balance exercise using WBED immediately improved reactive postural control. Therefore, wearable exercise devices, such as WBED, may contribute to the prevention of falls and fall-related injuries.

Effects of photo-irradiation on mercury binding to dissolved organic matter: Insights from FT-IR and synchronous fluorescence two-dimensional correlation spectroscopy.

The binding interactions between Hg and dissolved organic matter (DOM) affect the fate and transport of Hg in the aquatic environment. Here, we investigate the effects of photo-irradiation on the binding characteristics of dissolved organic matter with Hg(II) using FT-IR and synchronous fluorescence two-dimensional correlation spectroscopy (2D-COS). Results showed that the binding of Hg(II) onto humic acid (HA) followed the order of humic-like fraction > fulvic-like fraction > protein-like fraction and photo-irradiation did not affect this order. The binding affinity of each site within the fluorescent fraction was affected by the photoreaction patterns. Pre-irradiation of HA before Hg(II) binding changed its structures and binding ability. UV irradiation showed a more obvious effect on Hg(II)-HA complexes than solar irradiation, and UV irradiation enhanced the reactivity of aromatic groups of HA. The amine or amide N-H of HA played a leading role in binding with Hg(II) in the dark, whereas the aromatic amine C-N became dominant after UV irradiation. In fulvic acid (FA), the aromatic hydrogen C-H played a leading role in Hg(II) binding in the dark, but solar irradiation promoted the binding ability of polysaccharide C-O and the carboxyl CO became dominant after UV irradiation. The response sensitivity of the fulvic-like fraction to Hg(II) was higher than that of the protein-like fraction in FA. Multiple types of sites binding to Hg(II) were verified in the fulvic-like fraction and protein-like fraction of FA. These findings provide new insight into photo-induced structural changes of DOM upon Hg binding.

Effect of jaw clenching on postural adjustments to a predictable external perturbation.

This study investigated the effect of jaw clenching on anticipatory postural adjustments (APAs) and reactive postural adjustments (RPAs). Eight healthy adults were exposed to predictable external perturbations with and without submaximal jaw clenching. We recorded the three-dimensional body kinematics, ground reaction forces, and electromyography (EMG) of 12 muscles. EMG onset, integrated EMG, and positions of the center-of-mass (COM) and center-of-pressure (COP) during the anticipatory and reactive phases of postural adjustments were computed and compared for the jaw clenching and control conditions. Jaw clenching resulted in an earlier onset of APAs and a greater amplitude of trunk and lower limb EMG activities in the APAs and RPAs. There were no differences in the COM and COP displacements after the perturbation. Jaw clenching is effective for enhancing APAs and RPAs, although it may not increase postural stability following predictable external perturbation in healthy adults.

Neurons in Primary Motor Cortex Encode External Perturbations during an Orientation Reaching Task.

When confronting an abrupt external perturbation force during movement, subjects continuously adjust their behaviors to adapt to changes. Such adaptation is of great importance for realizing flexible motor control in varied environments, but the potential cortical neuronal mechanisms behind it have not yet been elucidated. Aiming to reveal potential neural control system compensation for external disturbances, we applied an external orientation perturbation while monkeys performed an orientation reaching task and simultaneously recorded the neural activity in the primary motor cortex (M1). We found that a subpopulation of neurons in the primary motor cortex specially created a time-locked activity in response to a "go" signal in the adaptation phase of the impending orientation perturbation and did not react to a "go" signal under the normal task condition without perturbation. Such neuronal activity was amplified as the alteration was processed and retained in the extinction phase; then, the activity gradually faded out. The increases in activity during the adaptation to the orientation perturbation may prepare the system for the impending response. Our work provides important evidence for understanding how the motor cortex responds to external perturbations and should advance research about the neurophysiological mechanisms underlying motor learning and adaptation.

Effect of dual tasking on anticipatory and compensatory postural adjustments in response to external perturbations in individuals with nonspecific chronic low back pain: Electromyographic analysis.

BACKGROUND: In patients with chronic low back pain (CLBP), postural control is a demanding task in terms of attention. Although the attentional demands of postural control have been investigated in these patients, the attentional demands of postural recovery during dual task performance have not been evaluated in patients with nonspecific CLBP. OBJECTIVE: To investigate the effect of dual tasking on anticipatory and compensatory postural adjustments in response to an external perturbation in patients with nonspecific CLBP. METHODS: Twenty-five patients with nonspecific CLBP of at least 3 months' duration and 25 healthy persons were exposed to predictable and unpredictable external perturbations. The attentional demands of postural adjustments were evaluated while participants simultaneously performed a cognitive task. Onset latency and integrated electromyographic activity of the trunk and leg muscles were compared between dual task (postural recovery and backward digit span memory) and single task conditions (postural recovery only). RESULTS: The results showed delayed activation of the tibialis anterior (agonist) and early activation of the gastrocnemius (antagonist) muscles during the dual task in patients with nonspecific CLBP compared to healthy participants. Integrated electromyographic activity was significantly greater in the dual task than the single task condition in the gastrocnemius (antagonist) muscle in patients with nonspecific CLBP compared to healthy persons during unpredictable perturbations. CONCLUSION: The impaired ankle muscle activities during a cognitive task suggest that postural control recovery following external perturbation requires attentional resources in patients with nonspecific CLBP. This may increase the risk of re-injury in people with nonspecific CLBP while they perform an attentionally demanding task in more difficult circumstances.

Physiological arousal accompanying postural responses to external perturbations after stroke.

OBJECTIVE: The purpose of this study was to examine simultaneously the level of physiological arousal and the postural response to external perturbations in people post-stroke compared to age-matched controls to build a more comprehensive understanding of the effect of stroke on postural control and balance self-efficacy. METHODS: Participants stood with each foot on separate force platforms. Ten applications of loads of 2% body weight at the hips perturbed the participant anteriorly under two conditions: investigator-triggered or self-triggered (total 20). Electrodermal activity (EDA; measurement of physiological arousal), electromyography (EMG) of the ankle plantarflexor muscles and anterior-posterior center of pressure measurements were taken pre-perturbation (anticipatory) and post-perturbation (response) and compared between the initial (first two) and final (last two) perturbations. RESULTS: Participants post-stroke demonstrated significantly higher levels of anticipatory EDA and anticipatory paretic plantarflexor EMG during both self- and investigator-triggered conditions compared to controls. Anticipatory EDA levels were higher in the final perturbations in participants post-stroke in both conditions, but not in controls. Habituation of the EDA responses post-perturbation was exhibited in the self-triggered perturbations in controls, but not in participants post-stroke. CONCLUSIONS: Physiological arousal and postural control strategies of controls revealed habituation in response to self-triggered perturbations, whereas this was not seen in participants post-stroke. SIGNIFICANCE: Understanding the physiological arousal response to challenges to standing balance post-stroke furthers our understanding of postural control mechanisms post-stroke.

Influence of wearing an unstable shoe construction on compensatory control of posture.

This study investigated the influence of wearing unstable shoe construction (WUS) on compensatory postural adjustments (CPA) associated with external perturbations. Thirty-two subjects stood on a force platform resisting an anterior-posterior horizontal force applied to a pelvic belt via a cable, which was suddenly released. They stood under two conditions: barefoot and WUS. The electromyographic (EMG) activity of gastrocnemius medialis, tibialis anterior, rectus femoris, biceps femoris, rectus abdominis, and erector spinae muscles and the center of pressure (CoP) displacement were acquired to study CPA. The EMG signal was used to assess individual muscle activity and latency, antagonist co-activation and reciprocal activation at joint and muscle group levels. Compared to barefoot, WUS led to: (1) increased gastrocnemius medialis activity, (2) increased total agonist activity, (3) decreased antagonist co-activation at the ankle joint and muscle group levels, (4) increased reciprocal activation at the ankle joint and muscle group levels, and (5) decrease in all muscle latencies. No differences were observed in CoP displacement between conditions. These findings demonstrate that WUS led to a reorganization of the postural control system associated to improved performance of some components of postural control responses.