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1.
Nat Rev Chem ; 8(5): 376-400, 2024 May.
Article in English | MEDLINE | ID: mdl-38693313

ABSTRACT

Electrification to reduce or eliminate greenhouse gas emissions is essential to mitigate climate change. However, a substantial portion of our manufacturing and transportation infrastructure will be difficult to electrify and/or will continue to use carbon as a key component, including areas in aviation, heavy-duty and marine transportation, and the chemical industry. In this Roadmap, we explore how multidisciplinary approaches will enable us to close the carbon cycle and create a circular economy by defossilizing these difficult-to-electrify areas and those that will continue to need carbon. We discuss two approaches for this: developing carbon alternatives and improving our ability to reuse carbon, enabled by separations. Furthermore, we posit that co-design and use-driven fundamental science are essential to reach aggressive greenhouse gas reduction targets.

2.
Gait Posture ; 107: 246-252, 2024 01.
Article in English | MEDLINE | ID: mdl-37923642

ABSTRACT

BACKGROUND: Ankle dorsiflexion function during swing phase contributes to foot clearance and plays an important role in walking ability post-stroke. Commonly used biomechanical measures such as foot clearance and ankle joint excursion have limited ability to accurately evaluate impaired dorsiflexor function. RESEARCH QUESTION: Can ankle angular velocity and acceleration be used as reliable measurers of dorsiflexion function in post-stroke gait? METHODS: Using linear regression and Pearson's correlation we retrospectively compared peak ankle angular velocity (AωP), peak ankle angular acceleration (AαP), peak dorsiflexion angle (DFAP) and peak foot clearance (FCLP) as direct measures for swing phase dorsiflexor function in 60 chronic stroke survivors. Intraclass correlation coefficient (ICC) analysis was used for test-retest reliability of AωP and AαP. RESULTS: Linear regression models revealed that AωP, AαP, DFAP, FCLP had a significant relationship (p < 0.05) with impaired dorsiflexion function. AαP and DFAP accounted for the most variance of dorsiflexion function. AωP, AαP, FCLP, correlated significantly with all clinical outcome measures of walking ability. DFAP had a positive correlation only with FMA-LE. Post-hoc William's t-tests, used to compare the magnitude of difference between two non-independent correlations, revealed that the correlation between all clinical measures and DFAP were significantly weaker than with AωP and AαP. Correlation between FMA-LE and FCLP was weaker than with AωP and AαP. Excellent test-retest reliability for both AωP (ICC = 0.968) and AαP (ICC = 0.947) was observed. SIGNIFICANCE: These results suggest that DFAP may only be associated with dorsiflexion function during non-task specific isolated movements, but not during walking. FCLP is associated with dorsiflexion function and walking ability measures but not as strongly as AωP and AαP possibly because FCLP is influenced by contribution from hip and knee joint movements. Therefore, AωP and AαP are reliable measures and represent dorsiflexion function more accurately than DFAP, and FCLP.


Subject(s)
Ankle , Stroke , Humans , Reproducibility of Results , Retrospective Studies , Walking , Stroke/complications , Gait , Ankle Joint , Biomechanical Phenomena
3.
J Clin Med ; 12(18)2023 Sep 15.
Article in English | MEDLINE | ID: mdl-37762933

ABSTRACT

The purpose of this investigation was to elucidate the relationship between the resting motor threshold (rMT) and active motor threshold (aMT). A cross-sectional comparison of MTs measured at four states of lower extremity muscle activation was conducted: resting, 5% maximal voluntary contraction (MVC), 10%MVC, and standing. MTs were measured at the tibialis anterior in the ipsilesional and contralesional limbs in participants in the chronic phase (>6 months) of stroke (n = 11) and in the dominant limb of healthy controls (n = 11). To compare across activation levels, the responses were standardized using averaged peak-to-peak background electromyography (EMG) activity measured at 10%MVC + 2SD for each participant, in addition to the traditional 0.05 mV criterion for rMT (rMT50). In all participants, as muscle activation increased, the least square mean estimates of MTs decreased (contralesional: p = 0.008; ipsilesional: p = 0.0015, healthy dominant: p < 0.0001). In healthy controls, rMT50 was significantly different from all other MTs (p < 0.0344), while in stroke, there were no differences in either limb (p > 0.10). This investigation highlights the relationship between rMT and aMTs, which is important as many stroke survivors do not present with an rMT, necessitating the use of an aMT. Future works may consider the use of the standardized criterion that accounted for background EMG activity across activation levels.

4.
Nat Commun ; 14(1): 6068, 2023 Sep 28.
Article in English | MEDLINE | ID: mdl-37770428

ABSTRACT

Anisotropic and efficient transport of ions under external stimuli governs the operation and failure mechanisms of energy-conversion systems and microelectronics devices. However, fundamental understanding of ion hopping processes is impeded by the lack of atomically precise materials and probes that allow for the monitoring and control at the appropriate time- and length- scales. In this work, using in-situ transmission electron microscopy, we directly show that oxygen ion migration in vacancy ordered, semiconducting SrFeO2.5 epitaxial thin films can be guided to proceed through two distinctly different diffusion pathways, each resulting in different polymorphs of SrFeO2.75 with different ground electronic properties before reaching a fully oxidized, metallic SrFeO3 phase. The diffusion steps and reaction intermediates are revealed by means of ab-initio calculations. The principles of controlling oxygen diffusion pathways and reaction intermediates demonstrated here may advance the rational design of structurally ordered oxides for tailored applications and provide insights for developing devices with multiple states of regulation.

5.
J Hazard Mater ; 459: 132165, 2023 Oct 05.
Article in English | MEDLINE | ID: mdl-37531768

ABSTRACT

Mechanism of hexavalent chromium removal (Cr(VI) as CrO42-) by the weak-base ion exchange (IX) resin ResinTech® SIR-700-HP (SIR-700) from simulated groundwater is assessed in the presence of radioactive contaminants iodine-129 (as IO3-), uranium (U as uranyl UO22+), and technetium-99 (as TcO4-), and common environmental anions sulfate (SO42-) and chloride (Cl-). Batch tests using the acid sulfate form of SIR-700 demonstrated Cr(VI) and U(VI) removal exceeded 97%, except in the presence of high SO42- concentrations (536 mg/L) where Cr(VI) and U(VI) removal decreased to ≥ 80%. However, Cr(VI) removal notably improved with co-mingled U(VI) that complexes with SO42- at the protonated amine sites. These U-SO42- complexes are integral to U(VI) removal, as confirmed by the decrease in U(VI) removal (<40%) when the acid chloride form of SIR-700 was used instead. Solid phase characterization revealed that CrO42- is removed by IX with SO42- complexes and/or reduced to amorphous Cr(III)(OH)3 at secondary alcohol sites. Tc(VII)O4- and I(V)O3- also undergo chemical reduction, following a similar removal mechanism. Oxyanion removal preference is determined by the anion reduction potential (CrO42->TcO4->IO3-), geometry, and charge density. For these reasons, 39% and 69% of TcO4- and 17% and 39% of IO3- are removed in the presence and absence of Cr(VI), respectively.

7.
bioRxiv ; 2023 Apr 30.
Article in English | MEDLINE | ID: mdl-37162884

ABSTRACT

Ankle dorsiflexion function during swing phase of the gait cycle contributes to foot clearance and plays an important role in walking ability post-stroke. Commonly used biomechanical measures such as foot clearance and ankle joint excursion have limited ability to accurately evaluate dorsiflexor function in stroke gait. We retrospectively evaluated ankle angular velocity and ankle angular acceleration as direct measures for swing phase dorsiflexor function in post-stroke gait of 61 chronic stroke survivors. Our linear regression models revealed that peak ankle angular velocity (AAV P ), peak ankle angular acceleration (AAA P ), peak dorsiflexion angle (DFA P ) and peak foot clearance (FCL P ) during swing had a significant relationship (p < 0.05) with impaired dorsiflexion function. AAA P and DFA P accounted for the most variance of dorsiflexion function. Additionally, AAV P , AAA P , FCL P during swing, correlated significantly with all clinical outcome measures of walking ability. DFA P during swing had a positive correlation only with FMA-LE. Post-hoc William's t -tests, used to compare the magnitude of difference between two non-independent correlations, revealed that the correlation between all clinical measures and DFA P were significantly weaker than with AAV P and AAA P . We also found that correlation between FMA-LE and FCL P was weaker than with AAV P and AAA P . We found an excellent test-retest reliability for both AAV P (ICC = 0.968) and AAA P (ICC = 0.947). These results suggest that DFA P may only be associated with non-task specific isolated dorsiflexion movement, but not during walking. FCL P is associated with dorsiflexion function and walking ability measures but not as strongly as AAV P and AAA P possibly because FCL P is influenced by contribution from hip and knee joint movements during walking. Therefore, we believe that AAV P and AAA P both can be used as reliable measures of impaired dorsiflexion function in post-stroke gait.

8.
Angew Chem Int Ed Engl ; 62(28): e202303770, 2023 Jul 10.
Article in English | MEDLINE | ID: mdl-37145989

ABSTRACT

Hierarchical nucleation pathways are ubiquitous in the synthesis of minerals and materials. In the case of zeolites and metal-organic frameworks, pre-organized multi-ion "secondary building units" (SBUs) have been proposed as fundamental building blocks. However, detailing the progress of multi-step reaction mechanisms from monomeric species to stable crystals and defining the structures of the SBUs remains an unmet challenge. Combining in situ nuclear magnetic resonance, small-angle X-ray scattering, and atomic force microscopy, we show that crystallization of the framework silicate, cyclosilicate hydrate, occurs through an assembly of cubic octameric Q3 8 polyanions formed through cross-linking and polymerization of smaller silicate monomers and other oligomers. These Q3 8 are stabilized by hydrogen bonds with surrounding H2 O and tetramethylammonium ions (TMA+ ). When Q3 8 levels reach a threshold of ≈32 % of the total silicate species, nucleation occurs. Further growth proceeds through the incorporation of [(TMA)x (Q3 8 )⋅n H2 O](x-8) clathrate complexes into step edges on the crystals.

9.
Angew Chem Int Ed Engl ; 62(30): e202304648, 2023 Jul 24.
Article in English | MEDLINE | ID: mdl-37221959

ABSTRACT

Mechanistic studies of substrate insertion into dimeric [(NHC)CuH]2 (NHC=N-heterocyclic carbene) complexes with two bridging hydrides have been shown to require dimer dissociation to generate transient, highly reactive (NHC)Cu-H monomers in solution. Using single-crystal to single-crystal (SC-SC) transformations, we discovered a new pathway of stepwise insertion of CO2 into [(NHC)CuH]2 without complete dissociation of the dimer. The first CO2 insertion into dimeric [(IPr*OMe)CuH]2 (IPr*OMe=N,N'-bis(2,6-bis(diphenylmethyl)-4-methoxy-phenyl)imidazole-2-ylidene) produced a dicopper formate hydride [(IPr*OMe)Cu]2 (µ-1,3-O2 CH)(µ-H). A second CO2 insertion produced a dicopper bis(formate), [(IPr*OMe)Cu]2 (µ-1,3-O2 CH)(µ-1,1-O2 CH), containing two different bonding modes of the bridging formate. These dicopper formate complexes are inaccessible from solution reactions since the dicopper core cleanly ruptures to monomeric complexes when dissolved in a solvent.

10.
J Clin Neurophysiol ; 2023 Mar 10.
Article in English | MEDLINE | ID: mdl-36893382

ABSTRACT

PURPOSE: Poststroke fatigue (PSF) contributes to increased mortality and reduces participation in rehabilitative therapy. Although PSF's negative influences are well known, there are currently no effective evidence-based treatments for PSF. The lack of treatments is in part because of a dearth of PSF pathophysiological knowledge. Increasing our understanding of PSF's causes may facilitate and aid the development of effective therapies. METHODS: Twenty individuals, >6 months post stroke, participated in this cross-sectional study. Fourteen participants had clinically relevant pathological PSF, based on fatigue severity scale (FSS) scores (total score ≥36). Single-pulse and paired-pulse transcranial magnetic stimulation were used to measure hemispheric asymmetries in resting motor threshold, motor evoked potential amplitude, and intracortical facilitation (ICF). Asymmetry scores were calculated as the ratios between lesioned and nonlesioned hemispheres. The asymmetries were then correlated (Spearman rho) to FSS scores. RESULTS: In individuals with pathological PSF (N = 14, range of total FSS scores 39-63), a strong positive correlation (rs = 0.77, P = 0.001) between FSS scores and ICF asymmetries was calculated. CONCLUSIONS: As the ratio of ICF between the lesioned and nonlesioned hemispheres increased so did self-reported fatigue severity in individuals with clinically relevant pathological PSF. This finding may implicate adaptive/maladaptive plasticity of the glutamatergic system/tone as a contributor to PSF. This finding also suggests that future PSF studies should incorporate measuring facilitatory activity and behavior in addition to the more commonly studied inhibitory mechanisms. Further investigations are required to replicate this finding and identify the causes of ICF asymmetries.

11.
Nanoscale ; 15(3): 1119-1127, 2023 Jan 19.
Article in English | MEDLINE | ID: mdl-36594352

ABSTRACT

Water electrolysis can use renewable electricity to produce green hydrogen, a portable fuel and sustainable chemical precursor. Improving electrolyzer efficiency hinges on the activity of the oxygen evolution reaction (OER) catalyst. Earth-abundant, ABO3-type perovskite oxides offer great compositional, structural, and electronic tunability, with previous studies showing compositional substitution can increase the OER activity drastically. However, the relationship between the tailored bulk composition and that of the surface, where OER occurs, remains unclear. Here, we study the effects of electrochemical cycling on the OER activity of La0.5Sr0.5Ni1-xFexO3-δ (x = 0-0.5) epitaxial films grown by oxide molecular beam epitaxy as a model Sr-containing perovskite oxide. Electrochemical testing and surface-sensitive spectroscopic analyses show Ni segregation, which is affected by electrochemical history, along with surface amorphization, coupled with changes in OER activity. Our findings highlight the importance of surface composition and electrochemical cycling conditions in understanding OER performance, suggesting common motifs of the active surface with high surface area systems.

12.
J Clin Neurophysiol ; 40(1): 71-78, 2023 Jan 01.
Article in English | MEDLINE | ID: mdl-34009847

ABSTRACT

PURPOSE: Transcranial direct current stimulation (tDCS) has mixed effects on walking performance in individuals poststroke. This is likely the result of variations in tDCS electrode montages and individualized responses. The purpose of this study was to quantify the effects of a single session of tDCS using various electrode montages on poststroke walking performance. METHODS: Individuals with chronic stroke ( n = 16) participated in a double-blind, randomized cross-over study with sham stimulation and three tDCS electrode montages. Gait speed, paretic step ratio, and paretic propulsion were assessed prestimulation and poststimulation at self-selected and fastest comfortable speeds. Changes in muscle activation patterns with self-selected walking were quantified by the number of modules derived from nonnegative matrix factorization of EMG signals for hypothesis generation. RESULTS: There was no significant effect of active stimulation montages compared with sham. Comparisons between each participant's best response to tDCS and sham show personalized tDCS may have a positive effect on fastest comfortable overground gait speed ( P = 0.084), paretic step ratio ( P = 0.095) and paretic propulsion ( P = 0.090), and self-selected paretic step ratio ( P = 0.012). Participants with two or three modules at baseline increased module number in response to the all experimental montages and sham, but responses were highly variable. CONCLUSIONS: A single session of tDCS may affect clinical and biomechanical walking performance, but effects seem to be dependent on individual response variability to different electrode montages. Findings of this study are consistent with responses to various tDCS electrode montages being the result of underlying neuropathology, and the authors recommend examining how individual factors affect responses to tDCS.


Subject(s)
Stroke , Transcranial Direct Current Stimulation , Humans , Electrodes , Stroke/therapy , Walking/physiology
13.
Arch Rehabil Res Clin Transl ; 5(4): 100296, 2023 Dec.
Article in English | MEDLINE | ID: mdl-38163035

ABSTRACT

Objective: To determine whether the measurement properties of an instrument that combines items from the Berg Balance Scale (BBS) and the Functional Gait Assessment (FGA) called the Functional Balance Ability Measure (FBAM) supports measuring balance across the functional mobility spectrum. Design: Retrospective cohort. Setting: Item-level data were from an archival research database. Participants: Ambulatory individuals (N=93, BBS=50 [29-56], FGA=16 [0-30], Fugl-Meyer Assessment of Lower Extremities=27 [14-34], self-selected walking speed=0.4±0.2 m/s, mean age ± SD, 61.7±11.3y; 30.1% female) with chronic stroke (≥6 months). Interventions: Not applicable. Main Outcome Measures: Unidimensionality was evaluated with a principal components analysis (PCA) of residuals. FBAM rating-scale characteristics, item hierarchy, item and person fit, and person separation were investigated using the Andrich Rating Scale Model. Results: PCA findings indicate the FBAM is sufficiently unidimensional. Rating scale structure was appropriate without modifying the original BBS and FGA scoring systems. Item hierarchy aligned with clinical and theoretical predictions (hardest item: FGA-gait with narrow base of support, easiest item: BBS-sitting unsupported). One item (BBS-standing on 1 foot) misfit, however, removal marginally affected person measures and model statistics. The FBAM demonstrated high person reliability (0.9) and 6 people (∼6%) misfit the expected response pattern. The FBAM separated participants into 4 statistically distinct strata, without a floor or ceiling effect. Conclusions: The FBAM is a unidimensional measure for balance ability across a continuum of functional tasks. Rating-scale characteristics, item hierarchy, item and person fit, and person separation support the FBAM's measurement properties in persons with chronic stroke. Future work should investigate measurement with fewer items and whether the FBAM addresses barriers to adoption of standardized balance measures in clinical practice.

14.
Sci Adv ; 8(51): eadd5328, 2022 Dec 23.
Article in English | MEDLINE | ID: mdl-36563139

ABSTRACT

The epitaxial growth of functional oxides using a substrate with a graphene layer is a highly desirable method for improving structural quality and obtaining freestanding epitaxial nanomembranes for scientific study, applications, and economical reuse of substrates. However, the aggressive oxidizing conditions typically used in growing epitaxial oxides can damage graphene. Here, we demonstrate the successful use of hybrid molecular beam epitaxy for SrTiO3 growth that does not require an independent oxygen source, thus avoiding graphene damage. This approach produces epitaxial films with self-regulating cation stoichiometry. Furthermore, the film (46-nm-thick SrTiO3) can be exfoliated and transferred to foreign substrates. These results open the door to future studies of previously unattainable freestanding oxide nanomembranes grown in an adsorption-controlled manner by hybrid molecular beam epitaxy. This approach has potentially important implications for the commercial application of perovskite oxides in flexible electronics and as a dielectric in van der Waals thin-film electronics.

15.
mSystems ; 7(6): e0091322, 2022 12 20.
Article in English | MEDLINE | ID: mdl-36394319

ABSTRACT

Soil fungi facilitate the translocation of inorganic nutrients from soil minerals to other microorganisms and plants. This ability is particularly advantageous in impoverished soils because fungal mycelial networks can bridge otherwise spatially disconnected and inaccessible nutrient hot spots. However, the molecular mechanisms underlying fungal mineral weathering and transport through soil remains poorly understood primarily due to the lack of a platform for spatially resolved analysis of biotic-driven mineral weathering. Here, we addressed this knowledge gap by demonstrating a mineral-doped soil micromodel platform where mineral weathering mechanisms can be studied. We directly visualize acquisition and transport of inorganic nutrients from minerals through fungal hyphae in the micromodel using a multimodal imaging approach. We found that Fusarium sp. strain DS 682, a representative of common saprotrophic soil fungus, exhibited a mechanosensory response (thigmotropism) around obstacles and through pore spaces (~12 µm) in the presence of minerals. The fungus incorporated and translocated potassium (K) from K-rich mineral interfaces, as evidenced by visualization of mineral-derived nutrient transport and unique K chemical moieties following fungus-induced mineral weathering. Specific membrane transport proteins were expressed in the fungus in the presence of minerals, including those involved in oxidative phosphorylation pathways and the transmembrane transport of small-molecular-weight organic acids. This study establishes the significance of a spatial visualization platform for investigating microbial induced mineral weathering at microbially relevant scales. Moreover, we demonstrate the importance of fungal biology and nutrient translocation in maintaining fungal growth under water and carbon limitations in a reduced-complexity soil-like microenvironment. IMPORTANCE Fungal species are foundational members of soil microbiomes, where their contributions in accessing and transporting vital nutrients is key for community resilience. To date, the molecular mechanisms underlying fungal mineral weathering and nutrient translocation in low-nutrient environments remain poorly resolved due to the lack of a platform for spatial analysis of biotic weathering processes. Here, we addressed this knowledge gap by developing a mineral-doped soil micromodel platform. We demonstrate the function of this platform by directly probing fungal growth using spatially resolved optical and chemical imaging methodologies. We found the presence of minerals was required for fungal thigmotropism around obstacles and through soil-like pore spaces, and this was related to fungal transport of potassium (K) and corresponding K speciation from K-rich minerals. These findings provide new evidence and visualization into hyphal transport of mineral-derived nutrients under nutrient and water stresses.


Subject(s)
Hyphae , Mycorrhizae , Hyphae/chemistry , Mycorrhizae/chemistry , Minerals/analysis , Potassium/analysis , Soil/chemistry
16.
Front Neurol ; 13: 968385, 2022.
Article in English | MEDLINE | ID: mdl-36388195

ABSTRACT

Background: Mass flexion-extension co-excitation patterns during walking are often seen as a consequence of stroke, but there is limited understanding of the specific contributions of different descending motor pathways toward their control. The corticospinal tract is a major descending motor pathway influencing the production of normal sequential muscle coactivation patterns for skilled movements. However, control of walking is also influenced by non-corticospinal pathways such as the corticoreticulospinal pathway that possibly contribute toward mass flexion-extension co-excitation patterns during walking. The current study sought to investigate the associations between damage to corticospinal (CST) and corticoreticular (CRP) motor pathways following stroke and the presence of mass flexion-extension patterns during walking as evaluated using module analysis. Methods: Seventeen healthy controls and 44 stroke survivors were included in the study. We used non-negative matrix factorization for module analysis of paretic leg electromyographic activity. We typically have observed four modules during walking in healthy individuals. Stroke survivors often have less independently timed modules, for example two-modules presented as mass flexion-extension pattern. We used diffusion tensor imaging-based analysis where streamlines connecting regions of interest between the cortex and brainstem were computed to evaluate CST and CRP integrity. We also used a coarse classification tree analysis to evaluate the relative CST and CRP contribution toward module control. Results: Interhemispheric CST asymmetry was associated with worse lower extremity Fugl-Meyer score (p = 0.023), propulsion symmetry (p = 0.016), and fewer modules (p = 0.028). Interhemispheric CRP asymmetry was associated with worse lower extremity Fugl-Meyer score (p = 0.009), Dynamic gait index (p = 0.035), Six-minute walk test (p = 0.020), Berg balance scale (p = 0.048), self-selected walking speed (p = 0.041), and propulsion symmetry (p = 0.001). The classification tree model reveled that substantial ipsilesional CRP or CST damage leads to a two-module pattern and poor walking ability with a trend toward increased compensatory contralesional CRP based control. Conclusion: Both CST and CRP are involved with control of modules during walking and damage to both may lead to greater reliance on the contralesional CRP, which may contribute to a two-module pattern and be associated with worse walking performance.

17.
Nat Chem ; 14(11): 1214-1223, 2022 Nov.
Article in English | MEDLINE | ID: mdl-36302871

ABSTRACT

Hydrogen has the highest gravimetric energy density of any energy carrier and produces water as the only oxidation product, making it extremely attractive for both transportation and stationary power applications. However, its low volumetric energy density causes considerable difficulties, inspiring intense efforts to develop chemical-based storage using metal hydrides, liquid organic hydrogen carriers and sorbents. The controlled uptake and release of hydrogen by these materials can be described as a series of challenges: optimal properties fall within a narrow range, can only be found in few materials and often involve important trade-offs. In addition, a greater understanding of the complex kinetics, mass transport and microstructural phenomena associated with hydrogen uptake and release is needed. The goal of this Perspective is to delineate potential use cases, define key challenges and show that solutions will involve a nexus of several subdisciplines of chemistry, including catalysis, data science, nanoscience, interfacial phenomena and dynamic or phase-change materials.

18.
Nano Lett ; 22(13): 5530-5537, 2022 Jul 13.
Article in English | MEDLINE | ID: mdl-35771509

ABSTRACT

Epitaxial growth is a powerful tool for synthesizing heterostructures and integrating multiple functionalities. However, interfacial mixing can readily occur and significantly modify the properties of layered structures, particularly for those containing energy storage materials with smaller cations. Here, we show a two-step sequence involving the growth of an epitaxial LiCoO2 cathode layer followed by the deposition of a binary transition metal oxide. Orientation-controlled epitaxial synthesis of the model solid-state-electrolyte Li2WO4 and anode material Li4Ti5O12 occurs as WO3 and TiO2 nucleate and react with Li ions from the underlying cathode. We demonstrate that this lithiation-assisted epitaxy approach can be used for energy materials discovery and exploring different combinations of epitaxial interfaces that can serve as well-defined model systems for mechanistic studies of energy storage and conversion processes.

19.
Phys Ther ; 102(8)2022 08 04.
Article in English | MEDLINE | ID: mdl-35670017

ABSTRACT

Interpreting change is a requisite component of clinical decision making for physical therapists. Physical therapists often interpret change using minimal detectable change (MDC) values. Current MDC formulas are informed by classical test theory and calculated with group-level error data. This approach assumes that measurement error is the same across a measure's scale and confines the MDC value to the sample characteristics of the study. Alternatively, an item response theory (IRT) approach calculates separate estimates of measurement error for different locations on a measure's scale. This generates a conditional measurement error for someone with a low, middle, or high score. Error estimates at the measure-level can then be used to determine a conditional MDC (cMDC) value for individual patients based on their unique pre- and post-score combination. cMDC values can supply clinicians with a means for using individual score data to interpret change scores while providing a personalized approach that should lower the threshold for change compared with the MDC and enhance the precision of care decisions by preventing misclassification of patients. The purpose of this Perspective is to present how IRT can address the limitations of MDCs for informing clinical practice. This Perspective demonstrates how cMDC values can be generated from item-level psychometrics derived from an IRT model using the patient-reported Activities-specific Balance Scale (ABC) commonly used in stroke rehabilitation and also illustrates how the cMDC compares to the MDC when accounting for changes in measurement error across a scale. Theoretical patient examples highlight how reliance on the MDC value can result in misclassification of patient change and how cMDC values can help prevent this from occurring. This personalized approach for interpreting change can be used by physical therapists to enhance the precision of care decisions.


Subject(s)
Physical Therapists , Stroke Rehabilitation , Disability Evaluation , Humans , Patient Reported Outcome Measures , Psychometrics , Reproducibility of Results
20.
Dalton Trans ; 51(18): 7268-7273, 2022 May 10.
Article in English | MEDLINE | ID: mdl-35475486

ABSTRACT

Coordination complexes of Mg(BH4)2 are of interest for energy storage, ranging from hydrogen storage in BH4 to electrochemical storage in Mg based batteries. Understanding the stability of these complexes is crucial since storage materials are expected to undergo multiple charging and discharging cycles. To do so, we examined the thermal stabilities of the 1 : 1 mixtures of Mg(BH4)2 with different glymes by DSC-TGA, TPD-MS and powder XRD analysis. Despite their structural similarities, these mixtures show diverse phase transitions, speciations and decomposition pathways as a function of linker length.

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