Participant experiences of eight weeks of supervised or home-based Pilates among people with multiple sclerosis: a qualitative analysis.

PURPOSE: An exploratory qualitative study investigating participants' experiences of a feasibility study of supervised and home-based Pilates. METHODS: All 10 females who participated in an eight-week supervised (n = 4) or home-based Pilates (n = 6) program were invited and agreed to be interviewed. Data were collected via semi-structured interviews and researcher observations of participant experiences. Data were analysed using codebook thematic analysis framework. RESULTS: Two domain summaries emerged: (1) the suitability of home-based Pilates in particular for this population. Participants indicated that supervised and home-based Pilates was a safe, intensity-appropriate, and implementable exercise method to improve mental health outcomes among persons with multiple sclerosis (PwMS), and (2) the benefits experienced by PwMS while participating in Pilates. Home-based Pilates reduced both exercise participation and accessibility barriers commonly experienced by PwMS. Furthermore, PwMS reported improvements in mental health outcomes following Pilates, in both exercise environments. CONCLUSIONS: PwMS reported experiencing improved mood following regular Pilates training and indicated that home-based in particular reduced barriers regularly experienced by this population. Results support Pilates as a feasible exercise modality providing potential mood improvements among PwMS. Future appropriately powered home-based randomised controlled trials to further explore the effects of Pilates training on mental health among PwMS with minimal-to-mild mobility disability are warranted.Implications for RehabilitationParticipants in this study described the mental health benefits experienced from engaging in Pilates, a non-traditional exercise modality.Home-based Pilates overcame participatory and accessibility barriers to exercise among people with multiple sclerosis (MS).Participants valued that Pilates was low intensity and did not exacerbate fatigue.Home-based Pilates is a feasible exercise method for people with MS with minimal-to-mild mobility disability.

Selective and Scalable Synthesis of Sugar Alcohols by Homogeneous Asymmetric Hydrogenation of Unprotected Ketoses.

Sugar alcohols are of great importance for the food industry and are promising building blocks for bio-based polymers. Industrially, they are produced by heterogeneous hydrogenation of sugars with H2 , usually with none to low stereoselectivities. Now, we present a homogeneous system based on commercially available components, which not only increases the overall yield, but also allows a wide range of unprotected ketoses to be diastereoselectively hydrogenated. Furthermore, the system is reliable on a multi-gram scale allowing sugar alcohols to be isolated in large quantities at high atom economy.

Ru0 or RuII: A Study on Stabilizing the "Activated" Form of Ru-PNP Complexes with Additional Phosphine Ligands in Alcohol Dehydrogenation and Ester Hydrogenation.

The complex Ru-MACHO has been previously shown to undergo uncontrolled degradation subsequent to base-induced dehydrochlorination in the absence of a substrate. In this study, we report that stabilization of the dehydrochlorinated Ru-MACHO with phosphines furnishes complexes whose structures depend on the phosphines employed: while PMe3 led to the expected octahedral RuII complex, PPh3 provided access to a trigonal-bipyramidal Ru0 complex. Because both complexes proved to be active in base-free (de)hydrogenation reactions, thorough quantum-chemical calculations were employed to understand the reaction mechanism. The calculations show that both complexes lead to the same mechanistic scenario after phosphine dissociation and, therefore, only differ energetically in this step. According to the calculations, the typically proposed metal-ligand cooperation mechanism is not the most viable pathway. Instead, a metal-ligand-assisted pathway is preferred. Finally, experiments show that phosphine addition enhances the catalyst's performance in comparison to the PR3-free "activated" Ru-MACHO.

Exploring unsymmetrical diboranes(4) as boryl ligand precursors: platinum(ii) bis-boryl complexes.

A series of five unsymmetrical platinum(ii) bis-boryl complexes, bearing two distinct boryl ligands, are obtained by the oxidative addition reaction of unsymmetrical diborane(4) derivatives, bearing either two different dialkoxy or one dialkoxy and one diamino boryl moiety, with [(Ph3P)2Pt(C2H4)]. All five complexes were structurally and spectroscopically characterised. The bis-boryl platinum(ii) complexes exhibit slightly distorted square-planar cis-boryl structures with acute B-Pt-B angles, short B⋯B distances of 2.44-2.55 Å and relatively long trans-boryl P-Pt distances around 2.34 Å. The 31P-195Pt NMR coupling constants are indicative for the strongly donating/trans-influencing boryl ligands. Despite the structural and spectroscopic data at hand no finally conclusive order of the donor properties/trans-influence of the boryl ligands can be deduced on the basis of these data. This may be explained by an (residual) interaction of two boryl ligands.

Structure and Reactivity of Half-Sandwich Rh(+3) and Ir(+3) Carbene Complexes. Catalytic Metathesis of Azobenzene Derivatives.

Traditional rhodium carbene chemistry relies on the controlled decomposition of diazo derivatives with [Rh2(OAc)4] or related dinuclear Rh(+2) complexes, whereas the use of other rhodium sources is much less developed. It is now shown that half-sandwich carbene species derived from [Cp*MX2]2 (M = Rh, Ir; X = Cl, Br, I, Cp* = pentamethylcyclopentadienyl) also exhibit favorable application profiles. Interestingly, the anionic ligand X proved to be a critical determinant of reactivity in the case of cyclopropanation, epoxide formation and the previously unknown catalytic metathesis of azobenzene derivatives, whereas the nature of X does not play any significant role in -OH insertion reactions. This perplexing disparity can be explained on the basis of spectral and crystallographic data of a representative set of carbene complexes of this type, which could be isolated despite their pronounced electrophilicity. Specifically, the donor/acceptor carbene 10a derived from ArC(═N2)COOMe and [Cp*RhCl2]2 undergoes spontaneous 1,2-migratory insertion of the emerging carbene unit into the Rh-Cl bond with formation of the C-metalated rhodium enolate 11. In contrast, the analogous complexes 10b,c derived from [Cp*RhX2]2 (X = Br, I) as well as the iridium species 13 and 14 derived from [Cp*IrCl2]2 are sufficiently stable and allow true carbene reactivity to be harnessed. These complexes are competent intermediates for the catalytic metathesis of azobenzene derivatives, which provides access to α-imino esters that would be difficult to make otherwise. Rather than involving metal nitrenes, the reaction proceeds via aza-ylides that evolve into diaziridines; a metastable compound of this type has been fully characterized.

Analyzing site selectivity in Rh2(esp)2-catalyzed intermolecular C-H amination reactions.

Predicting site selectivity in C-H bond oxidation reactions involving heteroatom transfer is challenged by the small energetic differences between disparate bond types and the subtle interplay of steric and electronic effects that influence reactivity. Herein, the factors governing selective Rh2(esp)2-catalyzed C-H amination of isoamylbenzene derivatives are investigated, where modification to both the nitrogen source, a sulfamate ester, and substrate are shown to impact isomeric product ratios. Linear regression mathematical modeling is used to define a relationship that equates both IR stretching parameters and Hammett σ(+) values to the differential free energy of benzylic versus tertiary C-H amination. This model has informed the development of a novel sulfamate ester, which affords the highest benzylic-to-tertiary site selectivity (9.5:1) observed for this system.