This pilot study aimed to investigate the relative and absolute reliability of variables obtained from an acceleration-based gait analysis conducted at comfortable and maximal gait speeds in individuals with chronic stroke. [Participants and Methods] This study included 25 community-dwelling individuals with chronic stroke. The participants wore triaxial accelerometers, while an observed walking trial was performed at comfortable and maximal speeds on two separate days 1 week apart. Relative reliability was evaluated using the intraclass correlation coefficient, and absolute reliability was evaluated using the Bland-Altman analysis, standard error of measurement, and minimal detectable change.[Results] The intraclass correlation coefficient of gait varied according to the acceleration-based gait analysis, ranging from 0.70 to 0.99. The Bland-Altman analysis revealed no systematic bias in both comfortable and maximal gait speed conditions. Most of the minimal detectable changes were smaller at maximal gait speed than at comfortable gait speed. [Conclusion] Acceleration-based gait analysis is a reliable method, particularly in maximal gait speed conditions. It may be used to assess the effect of rehabilitation interventions in individuals with chronic stroke.
Six‐coordinate osmium(III) complexes coordinated by a cyclohexanediamine‐based tetradentate ligand [trans‐N,N′‐dimethyl‐N,N′‐bis(2‐pyridylmethyl)‐1,2‐cyclohexanediamine: BPMCN] are synthesized. The remaining two coordination sites are occupied by chloride (Cl–), triflate (OTf–), or hydroxide/water (OH–/H2O) to complete the octahedral osmium(III) centers; [OsIIIX2(BPMCN)]+ (X = Cl– or OTf–) and [OsIII(OH)(H2O)(BPMCN)]2+. The OsIII(OH)(H2O) complex catalyzes cis‐dihydroxylation and cis‐aminohydroxylation of styrene with hydrogen peroxide (H2O2) and chloramine‐T (TsNClNa) to yield the corresponding diol and aminoalcohol, respectively. The oxido‐hydroxido‐osmium(V) complex {[OsV(O)(OH)(BPMCN)]2+} is isolated as the active oxidant of the dihydroxylation. The oxidation of the OsIII(OH)(H2O) complex with chloramine‐T yields oxido‐aminato‐osmium(V) complex, [OsV(O)(NHTs)(BPMCN)]2+. Comparison of the crystal structure with those of the oxido‐hydroxido‐osmium(V) complex and related imido‐ and amino‐osmium complexes indicates that the –NHTs group works as a monoanionic aminate ligand and the osmium(V)–NHTs bond has a single bond character [Os–N; 2.058(4) Å]. The oxido‐aminato‐osmium(V) complex is revealed as the active oxidant for the aminohydroxylation by the direct reaction of the complex with styrene. The characterization of the complex allows us to propose the catalytic mechanism of the aminohydroxylation of alkenes.
Interaction of osmium tetroxide (OsO4) with a series of halide ions (X− = I−, Br−, Cl−, and F−) is examined. Stable 1:1 adducts, [OsO4(X)]− (1X), are formed in the case of Br−, Cl−, and F−, whereas redox reaction takes place with I− to give [OsVIIO4]− and I•. The adduct formation constant (KfX) increases as the basicity of the halide ion increases (Br− < Cl− < F−). Upon the adduct formation, the symmetric (ν(Os=O)sym) and asymmetric (ν(Os=O)asym) Os=O stretching vibration energies are lowered as compared with those of OsO4. The X-ray crystallographic analyses of the halide adducts indicate that the structural distortion of the osmium center from tetrahedron to trigonal bipyramid becomes larger as the KfX value becomes larger. 1F shows much higher reactivity compared with 1Br and 1Cl in the oxidation of benzyl alcohol to benzaldehyde, even though 1F has a lower reduction potential compared to 1Br and 1Cl. Mechanistic details of the alcohol oxidation reaction are evaluated by kinetic studies including Hammett analysis and kinetic deuterium isotope effect as well as by DFT calculations.
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