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Low-frequency peaks in the Raman spectra of amorphous poly(ether ether ketone) (PEEK) were investigated. An amorphous sample with zero crystallinity, as confirmed by wide-angle X-ray diffraction, was used in this study. In a previous study, two peaks were observed in the low-frequency Raman spectra of the crystallized samples. Among these, the peaks at 135 cm-1 disappeared for the amorphous sample. Meanwhile, for the first time, the peak at 50 cm-1 was observed in the crystallized sample. Similar to the peak at 135 cm-1, the peak at 50 cm-1 disappeared in the amorphous state, and its intensity increased with increasing crystallinity. The origins of the two peaks were associated with the Ph-CO-Ph-type intermolecular vibrational modes in the simulation. This suggests that the Ph-CO-Ph vibrational mode observed in the low-frequency region of PEEK was strongly influenced by the intermolecular order.
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BACKGROUND: Among ambulatory people with incomplete spinal cord injury (iSCI), balance deficits are a primary factor limiting participation in walking activities. There is broad recognition that effective interventions are needed to enhance walking balance following iSCI. Interventions that amplify self-generated movements (e.g., error augmentation) can accelerate motor learning by intensifying sensorimotor feedback and facilitating exploration of motor control strategies. These features may be beneficial for retraining walking balance after iSCI. We have developed a cable-driven robot that creates a movement amplification environment during treadmill walking. The robot applies a continuous, laterally-directed, force to the pelvis that is proportional in magnitude to real-time lateral velocity. Our purpose is to investigate the effects of locomotor training in this movement amplification environment on walking balance. We hypothesize that for ambulatory people with iSCI, locomotor training in a movement amplification environment will be more effective for improving walking balance and participation in walking activities than locomotor training in a natural environment (no applied external forces). METHODS: We are conducting a two-arm parallel-assignment intervention. We will enroll 36 ambulatory participants with chronic iSCI. Participants will be randomized into either a control or experimental group. Each group will receive 20 locomotor training sessions. Training will be performed in either a traditional treadmill environment (control) or in a movement amplification environment (experimental). We will assess changes using measures that span the International Classification of Functioning, Disability and Health (ICF) framework including 1) clinical outcome measures of gait, balance, and quality of life, 2) biomechanical assessments of walking balance, and 3) participation in walking activities quantified by number of steps taken per day. DISCUSSION: Training walking balance in people with iSCI by amplifying the individual's own movement during walking is a radical departure from current practice and may result in new strategies for addressing balance impairments. Knowledge gained from this study will expand our understanding of how people with iSCI improve walking balance and how an intervention targeting walking balance affects participation in walking activities. Successful outcomes could motivate development of clinically feasible tools to replicate the movement amplification environment within clinical settings. TRIAL REGISTRATION: NCT04340063.
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Marcha , Traumatismos da Medula Espinal , Traumatismos da Medula Espinal/reabilitação , Traumatismos da Medula Espinal/fisiopatologia , Humanos , Marcha/fisiologia , Adulto , Terapia por Exercício/métodos , Equilíbrio Postural/fisiologia , Caminhada/fisiologia , Masculino , Feminino , Robótica/métodos , Método Simples-Cego , Pessoa de Meia-Idade , Locomoção/fisiologiaRESUMO
During visuomotor learning, improvements in motor performance accompany changes in how people use vision. However, the dependencies between altered visual reliance and improvements in motor skill is unclear. The present studies used an online sequence learning task to quantify how changing the availability of visual information affected motor skill learning (Study One) and how changing motor skill affected visual reliance (Study Two). Participants used their keyboard to respond to targets falling vertically down a game screen. In Study One (n=49), the availability of visual information was altered by manipulating where the targets were visible on the screen. Three experimental groups practiced the task during full or limited vision conditions (when the targets were only visible in specific areas). We hypothesized that limiting visual information would reduce motor learning (i.e. the rate of improvement during training trial blocks). Instead, while participants performed worse during limited vision trials (p<0.001), there was no difference in learning rate (p=0.87). In Study Two (n=119), all participants practiced the task with full vision and their visual reliance (i.e., their performance change between full and limited vision conditions) was quantified before and after training. We hypothesized that with motor learning, visual reliance on future targets would increase, while visual reliance on the current targets would decrease. The results of Study Two partially support our hypotheses with visual reliance decreasing for all visual areas (p<0.001). Together, the results suggest changing motor skill alters how people use vision, but changing visual availability does not affect motor learning.
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Performance in stair-climbing is largely associated with disruptions to mobility and community participation in children with cerebral palsy (CP). It is important to understand the nature of motor impairments responsible for making stairs a challenge in children with bilateral CP to clarify underlying causes of impaired mobility. In pediatric clinical populations, sensitive measurements of movement quality can be captured during the initial step of stair ascent. Thus, the purpose of this study was to quantify the lower limb joint moments of children with bilateral CP during the stance phases of a step-up task. Participants performed multiple stepping trials in a university gait laboratory. Outcome measures included extensor support moments (the sum of hip, knee, and ankle sagittal plane moments), hip abduction moments, and their timing. We recruited seven participants per group. We found that peak support and hip abduction moments were similar in the bilateral CP group compared to the typical development (TD) group. We also found that children with bilateral CP timed their peak moments closer together and increasingly depended on the hip joint to complete the task, especially in their more affected (MA) lower limb. Our investigation highlights some underlying causes that may make stair climbing a challenge for the CP population, including a loss of selective voluntary motor control (SVMC), and provides a possible treatment approach to strengthen lower limb muscles.
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A series of photosensitizers comprised of both an inorganic and an organic chromophore are investigated in a joint synthetic, spectroscopic, and theoretical study. This bichromophoric design strategy provides a means by which to significantly increase the excited state lifetime by isolating the excited state away from the metal center following intersystem crossing. A variable bridging group is incorporated between the donor and acceptor units of the organic chromophore, and its influence on the excited state properties is explored. The Franck-Condon (FC) photophysics and subsequent excited state relaxation pathways are investigated with a suite of steady-state and time-resolved spectroscopic techniques in combination with scalar-relativistic quantum chemical calculations. It is demonstrated that the presence of an electronically conducting bridge that facilitates donor-acceptor communication is vital to generate long-lived (32 to 45 µs), charge-separated states with organic character. In contrast, when an insulating 1,2,3-triazole bridge is used, the excited state properties are dominated by the inorganic chromophore, with a notably shorter lifetime of 60 ns. This method of extending the lifetime of a molecular photosensitizer is, therefore, of interest for a range of molecular electronic devices and photophysical applications.
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The impact of environmental uncertainty on locomotor adaptation remains unclear. Environmental uncertainty could either aid locomotor adaptation by prompting protective control strategies that stabilize movements to assist learning or impede adaptation by reducing error sensitivity and fostering hesitance to pursue corrective movements. To explore this, we investigated participants' adaptation to a consistent force field after experiencing environmental uncertainty in the form of unpredictable balance perturbations. We compared the performance of this group (Perturbation) to the adaptive performance of a group that did not experience any unpredictable perturbations (Non-Perturbation). Perturbations were delivered using a cable-driven robotic device applying lateral forces to the pelvis. We assessed whole-body center of mass (COM) trajectory (COM signed deviation), anticipatory postural adjustments (COM lateral offset), and first step width. The Perturbation group exhibited larger disruptions in COM trajectory (greater COM signed deviations) than the Non-Perturbation group when first walking in the force field. While the COM signed deviations of both groups decreased towards baseline values, only the Non-Perturbation group returned to baseline levels. The Perturbation groups COM signed deviations remained higher, indicating they failed to fully adapt to the force field before the end. The Perturbation group also did not adapt their COM lateral offset to counter the predictable effects of the force field as the Non-Perturbation group did, and their first step width increased more slowly. Our findings suggest that exposure to unpredictable perturbations impeded future sensorimotor adaptations to consistent perturbations.
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Equilíbrio Postural , Caminhada , Humanos , Incerteza , Movimento , Aprendizagem , Fenômenos Biomecânicos , Adaptação Fisiológica , MarchaRESUMO
The effect of sheep milk and cow milk on the lipid composition of rat brain was investigated in two feeding experiments of 28-days duration. Total lipids of the rat brain were extracted using ethanol-hexane, and the fatty acids and phospholipid contents analysed using gas chromatography with flame ionization detection (GC-FID) and phosphorus-31 nuclear magnetic resonance (31P NMR). Furthermore, freeze-dried pooled samples were analysed using attenuated total reflectance Fourier Transform Infrared and Fourier Transform Raman Spectroscopy and analysed with multivariate methods. A significantly (P < 0.05) higher C18:2 content was found in the cow milk group compared with sheep milk-treated groups in Study one. In Study two, a significantly (P < 0.05) lower C16:0 content was present in the sheep milk-treated group compared to the control low Ca/P group. No significant (P > 0.05) differences were observed in the spectroscopy analyses. It is concluded that sheep and cow milks fed to rats for 28-days had a low effect on the brain lipidome.
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Ácidos Graxos , Leite , Bovinos , Feminino , Ratos , Animais , Ovinos , Leite/química , Ácidos Graxos/análise , Fosfolipídeos/análise , Espectroscopia de Infravermelho com Transformada de Fourier , Cromatografia GasosaRESUMO
Postnatally, severe vitamin D deficiency commonly results in rickets as well as potential defects in tooth mineralization. The effects of milder deficiency on oral health outcomes later in life are still unclear. This study used micro-computed tomography (µCT), energy dispersive X-ray analysis (EDX), and Raman spectroscopy to investigate mineral density, total density, and elemental composition of enamel and dentine in 63 exfoliated primary incisors from participants with known 25-hydroxyvitamin D levels (25-OHD) at birth. No differences in mineralization and chemical composition using µCT and EDX analysis were observed irrespective of 25-OHD status. Subtle structural differences were observed via Raman spectroscopy, with more crystalline enamel observed in those with sufficient 25-OHD at birth. Although subtle, the differences seen suggest further attention should be given to children with known milder levels of vitamin D deficiency in early life. © 2023 The Authors. Journal of Bone and Mineral Research published by Wiley Periodicals LLC on behalf of American Society for Bone and Mineral Research (ASBMR).
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Deficiência de Vitamina D , Vitamina D , Criança , Recém-Nascido , Humanos , Microtomografia por Raio-X , Minerais , Dente Decíduo , Densidade ÓsseaRESUMO
Performance in a single step has been suggested to be sensitive measure of movement quality in pediatric clinical populations. Although there is less information available in children with typical development, researchers have postulated the importance of analyzing the effect of body weight modulation on the initiation of stair ascent, especially during single limb stance where upright stability is most critical. The purpose of this study was to investigate the effect of load modulation from -20% to +15% of body weight on typical pediatric lower limb joint moments during a step-up task. Fourteen participants between 5-21 years with no known history of neurological or musculoskeletal concerns were recruited to perform multiple step-up trials. Peak extensor support and hip abduction moments were identified during the push-off and pull-up stance phases. Linear regressions were used to determine the relationship between peak moments and load. Mixed effects models were used to estimate the effect of load on hip, knee, and ankle percent contributions to peak support moments. There was a positive linear relationship between peak support moments and load in both stance phases, where these moments scaled with load. There was no relationship between peak hip abduction moments and load. While the ankle and knee were the primary contributors to the support moments, the hip contributed more than expected in the pull-up phase. Clinicians can use these results to contextualize movement differences in pediatric clinical populations including cerebral palsy and highlight potential target areas for rehabilitation for populations such as adolescent athletes.
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People use vision to inform motor control strategies during walking. With practice performing a target stepping task, people shift their gaze farther ahead, transitioning from watching their feet contact the target to looking for future target locations. The shift in gaze focus suggests the role of vision in motor control changes from emphasizing feedback to feedforward control. The present study examines whether changing visual fixation location is accompanied by a similar change in reliance upon visual information. Twenty healthy young adults practiced stepping on moving targets projected on the surface of a treadmill. Periodically, participants' visual reliance was probed by hiding stepping targets which inform feedback or feedforward (targets < or > 1.5 steps ahead, respectively) motor control strategies. We calculated visual reliance as the increase in step error when targets were hidden. We hypothesized that with practice, participant reliance on feedback visual information would decrease and their reliance on feedforward visual information would increase. Contrary to our hypothesis, participants became significantly more reliant on feedback visual information with practice (p < 0.001) but their reliance on feedforward visual information did not change (p = 0.49). Participants' reliance on visual information increased despite looking significantly farther ahead with practice (p < 0.016). Together, these results suggest that participants fixated on feedback information less. However, changes in fixation pattern did not reduce their reliance upon feedback information as stepping performance still significantly decreased when feedback information was removed after training. These findings provide important context for how the role of vision in controlling walking changes with practice.
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Fixação Ocular , Aprendizagem , Adulto Jovem , Humanos , Pé , CaminhadaRESUMO
Low-frequency Raman spectroscopy (LFRS) is a valuable tool to detect the solid state of amorphous and crystalline drugs in solid dosage forms and the transformation of drugs between different polymorphic forms. It has also been applied to track the solubilisation of solid drugs as suspensions in milk and infant formula during in vitro digestion. This study reports the use of LFRS as an approach to probe drug precipitation from a lipid-based drug delivery system (medium-chain self-nanoemulsifying drug delivery system, MC-SNEDDS) during in vitro digestion. Upon lipolysis of the digestible components in MC-SNEDDS containing fenofibrate as a model drug, sharp phonon peaks appeared at the low-frequency Raman spectral region (<200 cm-1), indicating the precipitation of fenofibrate in a crystalline form from the formulation. Two multivariate data analysis approaches (principal component analysis and partial least squares discriminant analysis) and one univariate analysis approach (band ratios) were explored to track these spectral changes over time. The low-frequency Raman data produces results in good agreement with in situ small angle X-ray scattering (SAXS) measurements with all data analysis approaches used, whereas the mid-frequency Raman requires the use of PLS-DA to gain similar results. This suggests that LFRS can be used as a complementary, and potentially more accessible, technique to SAXS to determine the kinetics of drug precipitation from lipid-based formulations.
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Background: There is evidence that ambulatory people with incomplete spinal cord injury (iSCI) have an impaired ability to control lateral motion of their whole-body center of mass (COM) during walking. This impairment is believed to contribute to functional deficits in gait and balance, however that relationship is unclear. Thus, this cross-sectional study examines the relationship between the ability to control lateral COM motion during walking and functional measures of gait and balance in people with iSCI. Methods: We assessed the ability to control lateral COM motion during walking and conducted clinical gait and balance outcome measures on 20 ambulatory adults with chronic iSCI (C1-T10 injury, American Spinal Injury Association Impairment Scale C or D). To assess their ability to control lateral COM motion, participants performed three treadmill walking trials. During each trial, real-time lateral COM position and a target lane were projected on the treadmill. Participants were instructed to keep their lateral COM position within the lane. If successful, an automated control algorithm progressively reduced the lane width, making the task more challenging. If unsuccessful, the lane width increased. The adaptive lane width was designed to challenge each participant's maximum capacity to control lateral COM motion during walking. To quantify control of lateral COM motion, we calculated lateral COM excursion during each gait cycle and then identified the minimum lateral COM excursion occurring during five consecutive gait cycles. Our clinical outcome measures were Berg Balance Scale (BBS), Timed Up and Go test (TUG), 10-Meter Walk Test (10MWT) and Functional Gait Assessment (FGA). We used a Spearman correlation analysis (ρ) to examine the relationship between minimum lateral COM excursion and clinical measures. Results: Minimum lateral COM excursion had significant moderate correlations with BBS (ρ = -0.54, p = 0.014), TUG (ρ = 0.59, p = 0.007), FGA (ρ = -0.59, p = 0.007), 10MWT-preferred (ρ = -0.59, p = 0.006) and 10MWT-fast (ρ = -0.68, p = 0.001). Conclusion: Control of lateral COM motion during walking is associated with a wide range of clinical gait and balance measures in people with iSCI. This finding suggests the ability to control lateral COM motion during walking could be a contributing factor to gait and balance in people with iSCI.
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A hexa-peri-hexabenzocoronene (HBC)-substituted dipyridophenazine (dppz) ligand (dppz-HBC) and its corresponding rhenium [Re(CO)3Cl] and ruthenium [Ru(bpy)2]2+ complexes were synthesized and characterized. The interplay of their various excited states was investigated using spectroscopic and computational techniques. Perturbation of the HBC was seen through a broadening and decreased intensity of the HBC absorption bands that dominate the absorption spectra. A delocalized, partial charge transfer state was shown through emission (520 nm) in the ligand and rhenium complex and is supported by time-dependent density functional theory calculations. Transient absorption measurements revealed the presence of dark states with a triplet delocalized state populated in the ligand, while in the complexes, longer-lived (2.3-2.5 µs) triplet HBC states could be accessed. The properties of the studied ligand and complexes provide insight into the future design of polyaromatic systems and add to the rich history of dppz systems.
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The vibrational and electronic properties of six systematically altered donor-acceptor dyes were investigated with density functional theory (DFT), spectroscopy, and electrochemical techniques. The dyes incorporated a carbazole donor connected to a dithieno[3,2-b:2',3'-d]thiophene linker at either the C2 (m) or C3 (p) position. Indane-based acceptors contained either dimalononitrile (IndCN), ketone and malononitrile (InOCN) or diketone (IndO) electron accepting groups. Molecular geometries modeled by DFT using the BLYP functional and def2-TZVP basis set showed planar geometries containing large, extended π-systems and produced Raman spectra consistent with the experimental data. Electronic absorption spectra had transitions with π-π* character at wavelengths below 325 nm and a charge transfer (CT) transition region from 500 to 700 nm. The peak wavelength was dependent on the donor and acceptor architecture, with each modulating the HOMO and LUMO levels, respectively, supported by TD-DFT estimates using the LC-ωPBE* functional and 6-31g(d) basis set. The compounds showed emission in solution with quantum yields ranging from 0.004 to 0.6 and lifetimes of less than 2 ns. These were assigned to either π-π* or CT emissive states. Signals attributed to CT states exhibited positive solvatochromism and thermochromism. The spectral emission behavior of each compound trended with the acceptor unit moieties, where malononitrile units lead to greater π-π* character and ketones exhibited greater CT character.
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The solid-state landscape of carbamazepine during its dehydration was explored using Raman spectroscopy in the low- (-300 to -15, 15 to 300) and mid- (300 to 1800 cm-1) frequency spectral regions. Carbamazepine dihydrate and forms I, III, and IV were also characterized using density functional theory with periodic boundary conditions and showed good agreement with experimental Raman spectra with mean average deviations less than 10 cm-1. The dehydration of carbamazepine dihydrate was examined under different temperatures (40, 45, 50, 55, and 60 °C). Principal component analysis and multivariate curve resolution were used to explore the transformation pathways of different solid-state forms during the dehydration of carbamazepine dihydrate. The low-frequency Raman domain was able to detect the rapid growth and subsequent decline of carbamazepine form IV, which was not as effectively observed by mid-frequency Raman spectroscopy. These results showcased the potential benefits of low-frequency Raman spectroscopy for pharmaceutical process monitoring and control.
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Raman and infrared spectroscopy, used as individual and low-level fused datasets, were evaluated to identify and quantify the presence of adulterants (palm oil, PO; ω-3 concentrates in ethyl ester, O3C and fish oil, FO) in krill oil. These datasets were qualitatively analysed with principal component analysis (PCA) and classified as adulterated or unadulterated using support vector machines (SVM). Using partial least squares regression (PLSR), it was possible to identify and quantify the adulterant present in the KO mixture. Raman spectroscopy performed better (r2 = 0.98; RMSEP = 2.3%) than IR spectroscopy (r2 = 0.91; RMSEP = 4.2%) for quantification of O3C in KO. A data fusion approach further improved the analysis with model performance for quantification of PO (r2 = 0.98; RMSEP = 2.7%) and FO (r2 = 0.76; RMSEP = 9.1%). This study demonstrates the potential use of Raman and IR spectroscopy to quantify adulterants present in KO.
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Euphausiacea , Animais , Espectrofotometria Infravermelho , Análise Espectral Raman , Análise dos Mínimos Quadrados , Contaminação de Alimentos/análiseRESUMO
In this article, I provide a narrative remembrance of the many early proof-of-concept studies that were performed at the Jones Institute for Reproductive Medicine in the late 1980s and early 1990s. A group, led by the late Dr. Gary Hodgen, piloted some of the ways gonadotropin-releasing hormone analogues are now being used clinically. We also put many different early peptide and small molecule (orally active) gonadotropin-releasing hormone antagonists through a battery of tests to explore their effects on male and female reproductive hormones. Most of the compounds we tested never reached the clinic because of various reasons. However, some have and are now making a difference in people's lives.
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Humans continuously modulate their control strategies during walking based on their ability to anticipate disturbances. However, how people adapt and use motor plans to create stable walking in unpredictable environments is not well understood. Our purpose was to investigate how people adapt motor plans when walking in a novel and unpredictable environment. We evaluated the whole-body center of mass (COM) trajectory of participants as they performed repetitions of a discrete goal-directed walking task during which a laterally-directed force field was applied to the COM. The force field was proportional in magnitude to forward walking velocity and randomly directed towards either the right or left each trial. We hypothesized that people would adapt a control strategy to reduce the COM lateral deviations created by the unpredictable force field. In support of our hypothesis, we found that with practice the magnitude of COM lateral deviation was reduced by 28% (force field left) and 44% (force field right). Participants adapted two distinct unilateral strategies, implemented regardless of if the force field was applied to the right or to the left, that collectively created a bilateral resistance to the unpredictable force field. These strategies included an anticipatory postural adjustment to resist against forces applied to the left, and a more lateral first step to resist against forces applied to the right. In addition, during catch trials when the force field was unexpectedly removed, participants exhibited trajectories similar to baseline trials. These findings were consistent with an impedance control strategy that provides a robust resistance to unpredictable perturbations. However, we also found evidence that participants made predictive adaptations in response to their immediate experience that persisted for three trials. Due to the unpredictable nature of the force field, this predictive strategy would sometimes result in greater lateral deviations when the prediction was incorrect. The presence of these competing control strategies may have long term benefits by allowing the nervous system to identify the best overall control strategy to use in a novel environment.