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1.
Commun Chem ; 7(1): 69, 2024 Apr 01.
Artículo en Inglés | MEDLINE | ID: mdl-38561400

RESUMEN

Mixed-potential-driven catalysis is expected to be a distinctive heterogeneous catalytic reaction that produces products different from those produced by thermal catalytic reactions without the application of external energy. Electrochemically, the mechanism is similar to that of corrosion. However, a theory that incorporates catalytic activity as a parameter has not been established. Herein, we report the theoretical framework of mixed-potential-driven catalysis, including exchange currents, as a parameter of catalytic activity. The mixed potential and partitioning of the overpotential were determined from the exchange current by applying the Butler-Volmer equation at a steady state far from equilibrium. Mixed-potential-driven catalysis is expected to open new areas not only in the concept of catalyst development but also in the field of energetics of biological enzymatic reactions.

2.
Physiother Theory Pract ; : 1-11, 2023 Nov 02.
Artículo en Inglés | MEDLINE | ID: mdl-37916486

RESUMEN

INTRODUCTION: Body lateropulsion (BL) is an active lateral tilt of the body during standing or walking that is thought to be affected by a lesion of the vestibulospinal tract (VST) and the subjective visual vertical (SVV) tilt. Interventions for BL have not been established. OBJECTIVE: We examined the effects of postural-control training with different sensory reweighting on standing postural control in a patient with BL. METHODS: The patient had BL to the left when standing or walking due to a left-side medullary and cerebellar infarct. This study was a single-subject A-B design with follow-up: Phase A was postural-control training with visual feedback; phase B provided reweighting plantar somatosensory information. Postural control, VST excitability, and SVV were measured. RESULTS: At baseline and phase A, the patient could not stand with eyes-closed on a rubber mat, but became able to stand in phase B. The mediolateral center of pressure (COP) position did not change significantly, but the COP velocity decreased significantly during phase B and the follow-up on the firm surface. VST excitability was lower on the BL versus the non-BL side, and the SVV deviated to the right throughout the study. CONCLUSION: Postural-control training with reweighting somatosensory information might improve postural control in a patient with BL.

3.
Clin Rehabil ; 37(11): 1559-1574, 2023 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-37122265

RESUMEN

OBJECTIVE: People exhibiting post-stroke lateropulsion actively push their body across the midline to the more affected side and/or resist weight shift toward the less affected side. Despite its prevalence and associated negative rehabilitation outcomes, no clinical practice guidelines exist for the rehabilitation of post-stroke lateropulsion. We aimed to develop consensus-based clinical practice recommendations for managing post-stroke lateropulsion using an international expert panel. DESIGN: This Delphi panel process conformed with Guidance on Conducting and Reporting Delphi Studies recommendations. PARTICIPANTS: Panel members had demonstrated clinical and/or scientific background in the rehabilitation of people with post-stroke lateropulsion. MAIN MEASURES: The process consisted of four electronic survey rounds. Round One consisted of 13 open questions. Subsequent rounds ascertained levels of agreement with statements derived from Round One. Consensus was defined a priori as ≥75% agreement (agree or strongly agree), or ≥70% agreement after excluding 'unsure' responses. RESULTS: Twenty participants completed all four rounds. Consensus was achieved regarding a total of 119 recommendations for rehabilitation approaches and considerations for rehabilitation delivery, positioning, managing fear of falling and fatigue, optimal therapy dose, and discharge planning. Statements for which 'some agreement' (50%-74% agreement) was achieved and those for which recommendations remain to be clarified were recorded. CONCLUSIONS: These recommendations build on existing evidence to guide the selection of interventions for post-stroke lateropulsion. Future research is required to elaborate specific rehabilitation strategies, consider the impact of additional cognitive and perceptual impairments, describe positioning options, and detail optimal therapy dose for people with lateropulsion.


Asunto(s)
Rehabilitación de Accidente Cerebrovascular , Accidente Cerebrovascular , Humanos , Accidentes por Caídas , Miedo , Accidente Cerebrovascular/complicaciones , Accidente Cerebrovascular/diagnóstico , Accidente Cerebrovascular/terapia , Resultado del Tratamiento , Técnica Delphi
4.
Nanomaterials (Basel) ; 13(5)2023 Mar 05.
Artículo en Inglés | MEDLINE | ID: mdl-36903824

RESUMEN

The energy storage performances of supercapacitors are expected to be enhanced by the use of nanostructured hierarchically micro/mesoporous hollow carbon materials based on their ultra-high specific surface areas and rapid diffusion of electrolyte ions through the interconnected channels of their mesoporous structures. In this work, we report the electrochemical supercapacitance properties of hollow carbon spheres prepared by high-temperature carbonization of self-assembled fullerene-ethylenediamine hollow spheres (FE-HS). FE-HS, having an average external diameter of 290 nm, an internal diameter of 65 nm, and a wall thickness of 225 nm, were prepared by using the dynamic liquid-liquid interfacial precipitation (DLLIP) method at ambient conditions of temperature and pressure. High temperature carbonization (at 700, 900, and 1100 °C) of the FE-HS yielded nanoporous (micro/mesoporous) hollow carbon spheres with large surface areas (612 to 1616 m2 g-1) and large pore volumes (0.925 to 1.346 cm3 g-1) dependent on the temperature applied. The sample obtained by carbonization of FE-HS at 900 °C (FE-HS_900) displayed optimum surface area and exhibited remarkable electrochemical electrical double-layer capacitance properties in aq. 1 M sulfuric acid due to its well-developed porosity, interconnected pore structure, and large surface area. For a three-electrode cell setup, a specific capacitance of 293 F g-1 at a 1 A g-1 current density, which is approximately 4 times greater than the specific capacitance of the starting material, FE-HS. The symmetric supercapacitor cell was assembled using FE-HS_900 and attained 164 F g-1 at 1 A g-1 with sustained 50% capacitance at 10 A g-1 accompanied by 96% cycle life and 98% coulombic efficiency after 10,000 consecutive charge/discharge cycles. The results demonstrate the excellent potential of these fullerene assemblies in the fabrication of nanoporous carbon materials with the extensive surface areas required for high-performance energy storage supercapacitor applications.

5.
Front Hum Neurosci ; 17: 1109690, 2023.
Artículo en Inglés | MEDLINE | ID: mdl-36816498

RESUMEN

Introduction: We conducted dynamic balance or static intervention on healthy young adults to examine the changes in lateral vestibulospinal tract (LVST) excitability and postural control that ensued following dynamic balance intervention and to investigate the correlation between these changes. Methods: Twenty-eight healthy young adults were randomly assigned to either the dynamic balance group or the control group. They performed either a dynamic balance or static intervention for 10 trials of 30 s each and were assessed for head jerks during the intervention to confirm adaptation to the intervention. The dynamic balance intervention consisted of maintaining balance on a horizontally unstable surface, whereas the control intervention involved standing in the same foot position as the dynamic balance intervention on a stable surface while completing a maze task. LVST excitability and postural stability were assessed before and after the interventions. LVST excitability was assessed as the change rate in the soleus H-reflex amplitude with galvanic vestibular stimulation (GVSH). The velocity and area of the center of pressure (COP) were examined in the eyes closed/foam rubber condition. Results: No significant main and interaction effects (task, time) were observed for GVSH and COP variables. In the dynamic balance intervention, head jerk significantly decreased, and GVSH-change and changes in head jerk and COP area were significantly negatively correlated. Discussion: The LVST excitability change for the dynamic balance intervention varied among the participants, although increased LVST excitability may have been related to increased postural stability.

6.
Langmuir ; 38(47): 14430-14438, 2022 Nov 29.
Artículo en Inglés | MEDLINE | ID: mdl-36377773

RESUMEN

The adsorption of CO2 on nitrogen-doped graphitic carbon materials, such as graphene nanosheet (GNS) powder and highly oriented pyrolytic graphite (HOPG), was comparatively studied using temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS). Desorption of CO2 was observed at approximately 380 K for both pyridinic-nitrogen (pyri-N)-doped GNS and pyri-N-doped HOPG samples in the TPD experiments, whereas no CO2 desorption was observed for graphitic nitrogen-doped HOPG. This indicated that only pyri-N species create identical CO2 adsorption sites on any graphitic carbon surface. The adsorption energies of CO2 on pyri-N-doped carbons were estimated between 101 and 108 kJ mol-1, indicating that chemisorption, rather than physisorption, took place. The CO2 adsorption/desorption process was reproducible in repeated measurements, and no CO2 dissociation occurred during the process, suggesting that it is a promising CO2 capturing material. The O 1s peak of the adsorbed CO2 clearly appeared at 531.5-532 eV in the XPS measurements. The N 1s peak of pyri-N did not change with CO2 adsorption, indicating that CO2 is not directly bound to pyri-N but is adsorbed on a carbon atom near the pyridinic nitrogen via the nonbonding pz orbital of the carbon atom.

7.
Angew Chem Int Ed Engl ; 61(51): e202212506, 2022 Dec 19.
Artículo en Inglés | MEDLINE | ID: mdl-36240783

RESUMEN

Although pyridinic-nitrogen (pyri-N) doped graphene is highly active for the oxygen reduction reaction (ORR) of fuel cells in alkaline media, the activity critically decreases under acidic conditions. We report on how to prevent the deactivation based on the mechanistic understanding that O 2 + p y r i - N H + + e - → O 2 , a + p y r i - N H ${{{\rm O}}_{2}+{\rm p}{\rm y}{\rm r}{\rm i}{\rm { -}}{\rm N}{{\rm H}}^{+}+{{\rm e}}^{-}{\to }_{\ }^{{\rm \ }}{{\rm O}}_{2,{\rm a}}+{\rm p}{\rm y}{\rm r}{\rm i}{\rm { -}}{\rm N}{\rm H}}$ governs the ORR kinetics. First, we considered that the deactivation is due to the hydration of pyri-NH+ , leading to a lower shift of the redox potential. Introducing the hydrophobic cavity prevented the hydration of pyri-NH+ but inhibited the proton transport. We then increased proton conductivity in the hydrophobic cavity by introducing SiO2 particles coated with ionic liquid polymer/Nafion® which kept the high onset potentials with an increased current density even in acidic media.

8.
Chem Asian J ; 17(20): e202200756, 2022 Oct 17.
Artículo en Inglés | MEDLINE | ID: mdl-35999179

RESUMEN

Nanomaterials with hollow structures are expected to exhibit new functionalities for materials engineering. Here we report the fabrication of fullerene (C60 ) spheres having different hollow structures by using a kinetically controlled liquid-liquid interfacial precipitation (KC-LLIP) method. For this purpose, 1,2-ethylenediamine (EDA) was used as a covalent cross-linker of C60 molecules to form C60 -EDA shells, while in-situ generated EDA-sulfur (EDA-S) droplets were applied as 'yolks' being eliminated by washing following formation of the yolk-shell structure, leading to hollow structures. Porous spheres, string hollow spheres, hollow spheres, and open hollow spheres have been synthesized by controlling the kinetics of nucleation of C60 -EDA and the template EDA-S growth. Isopropanol was used as an additive to control the discrepancy in growth rates of C60 -EDA and EDA-S. This simple KC-LLIP preparation method is expected to facilitate the large-scale fabrication and application of structured C60 spheres in materials science and technology.

9.
Sci Technol Adv Mater ; 23(1): 413-423, 2022.
Artículo en Inglés | MEDLINE | ID: mdl-35756168

RESUMEN

Electro-catalytic activity of Pt in the oxygen reduction reaction (ORR) depends strongly on its morphology. For an understanding of how morphology affects the catalytic properties of Pt, the investigation of Pt materials having well-defined morphologies is required. However, the challenges remain in rational and facile synthesis of Pt particles with tuneable well-defined morphology. A promising approach for the controlled synthesis of Pt particles is 'self-assembly of building blocks'. Here, we report a unique synthesis method to control Pt morphology by using a self-assembly route, where nanoflower, nanowire, nanosheet and nanotube morphologies of Pt particles have been produced in a controlled manner. In the growth mechanism, Pt nanoparticles (5-11 nm) are rapidly prepared by using NaBH4 as a reductant, followed by their agglomeration promoted by adding 1,2-ethylenediamine. The morphology of the resulting Pt particles can be easily controlled by tuning hydrophobic/hydrophilic interactions by the addition of isopropanol and H2O. Of the Pt particles prepared using this method, Pt nanotubes show the highest ORR catalytic activity in an acid electrolyte with an onset potential of 1.02 V vs. RHE.

10.
Ann Phys Rehabil Med ; 65(6): 101684, 2022 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-35667626

RESUMEN

Post-stroke lateropulsion is prevalent. The global inconsistency in terminology used to describe the condition presents obstacles in accurately comparing research results, reaching consensus on use of measurement tools, agreeing upon a consistent approach to rehabilitation, and translating research to clinical practice. Commencing in 2021, 20 international experts undertook a Delphi Process that aimed to compile clinical practice recommendations for the rehabilitation of lateropulsion. As a part of the process, the panel agreed to aim to reach consensus regarding terminology used to describe the condition. Improved understanding of the condition could lead to improved management, which will enhance patient outcomes after stroke and increase efficiency of healthcare resource utilisation. While consensus was not reached, the panel achieved some agreement that 'lateropulsion' is the preferred term to describe the phenomenon of 'active pushing of the body across the midline toward the more affected side, and / or actively resisting weight shift toward the less affected side'. This group recommends that 'lateropulsion' is used in future research and in clinical practice.


Asunto(s)
Rehabilitación de Accidente Cerebrovascular , Accidente Cerebrovascular , Humanos , Equilibrio Postural
11.
J Am Chem Soc ; 144(27): 12158-12166, 2022 Jul 13.
Artículo en Inglés | MEDLINE | ID: mdl-35762507

RESUMEN

The reaction mechanism of the CH3OH synthesis by the hydrogenation of CO2 on Cu catalysts is unclear because of the challenge in experimentally detecting reaction intermediates formed by the hydrogenation of adsorbed formate (HCOOa). Thus, the objective of this study is to clarify the reaction mechanism of the CH3OH synthesis by establishing the kinetic natures of intermediates formed by the hydrogenation of adsorbed HCOOa on Cu(111). We exposed HCOOa on Cu(111) to atomic hydrogen at low temperatures of 200-250 K and observed the species using infrared reflection absorption (IRA) spectroscopy and temperature-programmed desorption (TPD) studies. In the IRA spectra, a new peak was observed upon the exposure of HCOOa on Cu(111) to atomic hydrogen at 200 K and was assigned to the adsorbed dioxymethylene (H2COOa) species. The intensity of the new peak gradually decreased with heating from 200 to 290 K, whereas the IR peaks representing HCOOa species increased correspondingly. In addition, small amounts of formaldehyde (HCHO), which were formed by the exposure of HCOOa species to atomic hydrogen, were detected in the TPD studies. Therefore, H2COOa is formed via hydrogenation by atomic hydrogen, which thermally decomposes at ∼250 K on Cu(111). We propose a potential diagram of the CH3OH synthesis via H2COOa from CO2 on Cu surfaces, with the aid of density functional theory calculations and literature data, in which the hydrogenation of bidentate HCOOa to H2COOa is potentially the rate-determining step and accounts for the apparent activation energy of the methanol synthesis from CO2 on Cu surfaces.

12.
J Cent Nerv Syst Dis ; 14: 11795735221081599, 2022.
Artículo en Inglés | MEDLINE | ID: mdl-35237093

RESUMEN

Postural imbalance, abnormal axial posture, and axial rigidity are the characteristic features of Parkinson's disease (PD), and they are referred to as axial symptoms. The symptoms are difficult to manage since they are often resistant to both L-DOPA and deep brain stimulation. Hence, other treatments that can improve Parkinsonian axial symptoms without adverse effects are required. Vestibular dysfunction occurs in PD since neuropathological changes and reflex abnormalities are involved in the vestibular nucleus complex. Galvanic vestibular stimulation (GVS), which activates the vestibular system, is a noninvasive method. This review aimed to assess the clinical effect of GVS on axial symptoms in PD. To date, studies on the effects of GVS on postural instability, anterior bending posture, lateral bending posture, and trunk rigidity and akinesia in PD had yielded interesting data, and none of the patients presented with severe adverse events, and the others had mild reactions. GVS indicated a possible novel therapy. However, most included a small number of patients, and the sample sizes were not similar in some studies that included controls. In addition, there was only one randomized controlled clinical trial, and it did not perform an objective evaluation of axial symptoms. In this type of research, vestibular contributions to balance should be distinguished from others such as proprioceptive inputs or nonmotor symptoms of PD.

13.
Phys Chem Chem Phys ; 24(5): 2988-2996, 2022 Feb 02.
Artículo en Inglés | MEDLINE | ID: mdl-35037674

RESUMEN

We report a newly designed compact cell to measure XAFS spectra with the conversion electron yield (CEY) method in the soft X-ray region under ambient-pressure gas conditions. Secondary electrons generated from the gas and sample by collision of X-ray-absorption-induced Auger electrons are collected by a positively biased collector electrode to obtain XAFS spectra. It was confirmed that this cell is applicable to soft X-ray surface XAFS measurements for different types of materials such as insulating organic materials and metal oxides under 1 bar gas conditions. During the measurements, photoinduced side effects were observed; i.e. photoinduced degradation of organic materials and photoinduced reduction/oxidation of metal oxides. We found that these photoinduced side effects can be sufficiently suppressed by controlling the measuring conditions. The presented measuring approach will enable surface XAFS spectra to be obtained in the soft X-ray region for various types of functional materials under ambient-pressure working conditions.

14.
J Parkinsons Dis ; 11(4): 1619-1630, 2021.
Artículo en Inglés | MEDLINE | ID: mdl-34366377

RESUMEN

BACKGROUND: Long-term physiotherapy is acknowledged to be crucial to manage motor symptoms for Parkinson's disease (PD) patients, but its effectiveness is not well understood. OBJECTIVE: This systematic review and meta-analysis aimed to assess the evidence regarding the effectiveness of long-term physiotherapy to improve motor symptoms and reduce antiparkinsonian medication dose in PD patients. METHODS: Pubmed, Cochrane, PEDro, and CINAHL were searched for randomized controlled trials before August 31, 2020 that investigated the effectiveness of physiotherapy for 6 months or longer on motor symptoms and levodopa-equivalent dose (LED) in PD patients with Hoehn and Yahr stage 1- 3. We performed random effects meta-analyses for long-term physiotherapy versus no/control intervention and estimated standard mean differences with 95% confidence intervals (CIs). Levels of evidence were rated by the Grading of Recommendation Assessment, Development and Evaluation approach. RESULTS: From 2,940 studies, 10 studies involving 663 PD patients were assessed. Long-term physiotherapy had favorable effects on motor symptoms in off medication state [- 0.65, 95% CI - 1.04 to - 0.26, p = 0.001] and LED [- 0.49, 95% CI - 0.89to - 0.09, p = 0.02]. Subgroup analyses demonstrated favorable effects on motor symptoms in off medication state by aerobic exercise [- 0.42, 95% CI - 0.64 to - 0.20, p < 0.001] and LED by multidisciplinary rehabilitation of primarily physiotherapy [- 1.00, 95% CI - 1.44 to - 0.56, p < 0.001]. Quality of evidence for aerobic exercise and multidisciplinary rehabilitation were low and very low. CONCLUSION: This review provided evidence that long-term physiotherapy has beneficial impact on motor symptoms and antiparkinsonian medication dose in PD patients and could motivate implementation of long-term physiotherapy.


Asunto(s)
Antiparkinsonianos/farmacología , Enfermedad de Parkinson , Antiparkinsonianos/química , Humanos , Levodopa/química , Enfermedad de Parkinson/tratamiento farmacológico , Modalidades de Fisioterapia
15.
Neurosci Lett ; 755: 135910, 2021 06 11.
Artículo en Inglés | MEDLINE | ID: mdl-33910060

RESUMEN

The vestibulospinal tract (VST) plays an important role in the control of the ipsilateral antigravity muscles, and the balance of left and right VST excitability is important in human postural control. A method for measuring VST excitability is the application of galvanic vestibular stimulation (GVS) before tibial nerve stimulation that evokes the soleus H-reflex; the change rate of the H-reflex amplitude is then evaluated. Assessments of VST excitability and the left and right balance could be useful when determining the pathology for interventions in postural control impairments. However, the reliability and laterality of this assessment have not been clarified, nor has its relationship to postural control. We investigated the reliability, laterality and standing postural control in relation to the degree of facilitation of the H-reflex following GVS in 15 healthy adults. The assessments were performed in two sessions, one each for the left- and right-sides, in random order. The inter-session reliability of the short-interval assessments of an increase in the H-reflex following GVS on both sides were sufficient. The degree of H-reflex facilitation by GVS showed no significant difference between the left- and right-sides in any session. There was a moderate positive correlation between the mediolateral position of the center of pressure in the eyes-closed standing on foam condition and the left/right ratio of the degree of increased H-reflex in the first-session. We concluded that this method for evaluating the increase in the soleus H-reflex following GVS has high inter-session reliability in the short-interval that did not differ between sides.


Asunto(s)
Electromiografía/normas , Respuesta Galvánica de la Piel/fisiología , Reflejo H/fisiología , Músculo Esquelético/fisiología , Equilibrio Postural/fisiología , Tractos Espinocerebelares/fisiología , Adulto , Femenino , Voluntarios Sanos , Humanos , Masculino , Reproducibilidad de los Resultados , Médula Espinal/fisiología
16.
Front Hum Neurosci ; 15: 646127, 2021.
Artículo en Inglés | MEDLINE | ID: mdl-33679355

RESUMEN

OBJECTIVE: Noisy galvanic vestibular stimulation (nGVS) is often used to improve postural stability in disorders, such as neurorehabilitation montage. For the safe use of nGVS, we investigated whether arterial pressure (AP) and heart rate vary during static supine and slow whole-body tilt with random nGVS (0.4 mA, 0.1-640 Hz, gaussian distribution) in a healthy elderly population. METHODS: This study was conducted with a double-blind, sham-controlled, cross-over design. Seventeen healthy older adults were recruited. They were asked to maintain a static supine position on a bed for 10 min, and the bed was tilted up (TU) to 70 degrees within 30 s. After maintaining this position for 3 min, the bed was passively tilted down (TD) within 30 s. Real-nGVS or sham-nGVS was applied from 4 to 15 min. The time course of mean arterial pressure (MAP) and RR interval variability (RRIV) were analyzed to estimate the autonomic nervous activity. RESULT: nGVS and/or time, including pre-/post-event (nGVS-start, TU, and TD), had no impact on MAP and RRIV-related parameters. Further, there was no evidence supporting the argument that nGVS induces pain, vertigo/dizziness, and uncomfortable feeling. CONCLUSION: nGVS may not affect the AP and RRIV during static position and whole-body tilting or cause pain, vertigo/dizziness, and discomfort in the elderly.

17.
Exp Brain Res ; 239(3): 997-1007, 2021 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-33479869

RESUMEN

The human vestibulospinal tract has important roles in postural control, but it has been unknown whether vestibulospinal tract excitability is influenced by the body's postures. We investigated whether postures influence the vestibulospinal tract excitability by a neurophysiological method, i.e., applying galvanic vestibular stimulation (GVS) 100 ms before tibial nerve stimulation evoking the soleus H-reflex. GVS is a percutaneous stimulation, and it has not been clarified how the cutaneous input from GVS influences the facilitation effect of cathodal GVS on the soleus H-reflex amplitude. In Experiment 1, we evaluated the effects of GVS on the soleus H-reflex amplitude of subjects in the prone, supine, and sitting positions in random order to clarify the differences in the GVS effects among these postures. In Experiment 2, to determine whether the effects of GVS in the supine and sitting positions are due solely to cutaneous input from GVS, we provided GVS and cutaneous stimulations as conditioning stimuli and compared the effects in both postures. Interaction effects between postures and stimulus conditions were observed in both experiments. The facilitation rate of the maximum H-reflex amplitude by GVS in the sitting position was significantly higher than those in the prone and supine positions (Experiment 1). The facilitation rate of GVS was significantly larger than the cutaneous stimulation only in the sitting position (Experiment 2). These results indicate that vestibulospinal tract excitability may be higher in the sitting position than in either lying position (prone and supine), due mainly to the increased need for postural control.


Asunto(s)
Postura , Estimulación Eléctrica , Reflejo H , Humanos , Músculo Esquelético , Equilibrio Postural , Vestíbulo del Laberinto
18.
Phys Chem Chem Phys ; 23(13): 7724-7734, 2021 Apr 07.
Artículo en Inglés | MEDLINE | ID: mdl-32870215

RESUMEN

Two-dimensional hydrogen boride (HB) sheets were recently demonstrated to act as a solid acid catalyst in their hydrogen-deficient state. However, both the active sites and the mechanism of the catalytic process require further elucidation. In this study, we analyzed the conversion of ethanol adsorbed on HB sheets under vacuum during heating using in situ Fourier transform infrared (FT-IR) absorption spectroscopy with isotope labelling. Up to 450 K, the FT-IR peak associated with the OH group of the adsorbed ethanol molecule disappeared from the spectrum, which was attributed to a dehydration reaction with a hydrogen atom from the HB sheet, resulting in the formation of an ethyl species. At temperatures above 440 K, the number of BD bonds markedly increased in CD3CH2OH, compared to CH3CD2OH; the temperature dependence of the formation rate of BD bonds was similar to that of the dehydration reaction rate of ethanol on HB sheets under steady-state conditions. The rate-determining step of the dehydration of ethanol on HB was thus ascribed to the dehydrogenation of the methyl group of the ethyl species on the HB sheets, followed by the immediate desorption of ethylene. These results show that the catalytic ethanol dehydration process on HB involves the hydrogen atoms of the HB sheets. The obtained mechanistic insights are expected to promote the practical application of HB sheets as catalysts.

19.
Angew Chem Int Ed Engl ; 60(10): 5121-5124, 2021 Mar 01.
Artículo en Inglés | MEDLINE | ID: mdl-33174332

RESUMEN

The introduction of pyridinic nitrogen (pyri-N) into carbon-based electrocatalysts for the oxygen reduction reaction is considered to create new active sites. Herein, the role of pyri-N in such catalysts was investigated from a mechanistic viewpoint using carbon black (CB)-supported pyri-N-containing molecules as model catalysts; the highest activity was observed for 1,10-phenanthroline/CB. X-ray photoemission spectroscopy showed that in acidic electrolytes, both pyri-N atoms of 1,10-phenanthroline could be protonated to form pyridinium ions (pyri-NH+ ). In O2 -saturated electrolytes, one of the pyri-NH+ species was reduced to pyri-NH upon the application of a potential; no such reduction was observed in N2 -saturated electrolytes. This behavior was ascribed to electrochemical reduction of pyri-NH+ occurring simultaneously with the thermal adsorption of O2 , as supported by DFT calculations. According to these calculations, the coupled reduction was promoted by hydrophobic environments.

20.
Neurosci Lett ; 714: 134598, 2020 01 01.
Artículo en Inglés | MEDLINE | ID: mdl-31678433

RESUMEN

The body's subjective postural vertical (SPV) has been thought to be affected by somatosensory information. How the SPV is perceived based on what types of somatosensory information has not been determined experimentally by manipulating somatosensory conditions. We investigated the effects of disturbing the somatosensory information from a seat pad and/or vestibular sensory information on the SPV in 15 healthy adults. Their SPV values were measured under four conditions (control, somatosensory, vestibular, and somatosensory + vestibular) in random order. The average and absolute SPV values were measured. In the somatosensory condition, a foam rubber pad was placed on the seating surface and the subject's SPV was measured. In the vestibular condition, the SPV was measured during galvanic vestibular stimulation (GVS). The somatosensory + vestibular condition was used to measure the SPV during combined somatosensory and vestibular stimulation. The mean SPV value was significantly increased in the somatosensory + vestibular condition compared to the other three conditions. The absolute value of SPV was significantly increased in the somatosensory and somatosensory + vestibular conditions compared to the control and vestibular conditions. There was no significant difference in the average or absolute SPV values in the vestibular condition compared to the other conditions. There was no significant difference between SPV errors when somatosensory information was disturbed or when somatosensory + vestibular information was disturbed. When the somatosensory information from the seat was disturbed, the SPV error increased, and it also shifted under the influence of the vestibular sensory information modulation. These results indicate that somatosensory information from the seat plays an important role in SPV in healthy adults.


Asunto(s)
Estimulación Eléctrica/métodos , Sensación de Gravedad/fisiología , Propiocepción/fisiología , Rotación , Tacto/fisiología , Adulto , Femenino , Voluntarios Sanos , Humanos , Masculino , Estimulación Física/métodos
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