The Catalytic Enantioselective, Protecting Group-Free Total Synthesis of (+)-Dichroanone

Herein we report the first enantioselective total synthesis of (+)-dichroanone, confirming the absolute configuration of the natural product. This protecting group-free route features the first application of our enantioselective Tsuji allylation in the context of a natural product total synthesis. Additionally, this 11-step preparation of the molecule from commercial material features a novel Kumada-aromatization strategy and a rapid sequence for the conversion of a phenol to a hydroxy-p-benzoquinone

A Facile and Modular Synthesis of Phosphinooxazoline Ligands

The copper(I) iodide catalyzed phosphine/aryl halide coupling procedure of Buchwald et al. provides modular, robust, and scaleable access to phosphinooxazoline (PHOX) ligands. The advantages of this method are highlighted by the convenient synthesis of PHOX ligands with varied steric and electronic properties, which would be challenging to synthesize by other protocols

The Catalytic Enantioselective, Protecting Group-Free Total Synthesis of (+)-Dichroanone

Herein we report the first enantioselective total synthesis of (+)-dichroanone, confirming the absolute configuration of the natural product. This protecting group-free route features the first application of our enantioselective Tsuji allylation in the context of a natural product total synthesis. Additionally, this 11-step preparation of the molecule from commercial material features a novel Kumada-aromatization strategy and a rapid sequence for the conversion of a phenol to a hydroxy-p-benzoquinone

Depth-resolved measurements of the Meissner screening profile in surface-treated Nb

We report depth-resolved measurements of the Meissner screening profile in several surface-treated Nb samples using low-energy muon spin rotation (LE-$\mu$SR). In these experiments, implanted positive muons, whose stopping depths below Nb's surface were adjusted between ~10 nm to ~150 nm, reveal the field distribution inside the superconducting element via their spin-precession (communicated through their radioactive decay products). We compare how the field screening is modified by different surface treatments commonly employed to prepare superconducting radio frequency (SRF) cavities used in accelerator beamlines. In contrast to an earlier report [A. Romanenko et al., Appl. Phys. Lett. 104 072601 (2014)], we find no evidence for any "anomalous" modifications to the Meissner profiles, with all data being well-described by a London model. Differences in screening properties between surface treatments can be explained by changes to the carrier mean-free-paths resulting from dopant profiles near the material's surface.Comment: 15 pages, 5 figures, 2 table

The Palladium-Catalyzed Aerobic Kinetic Resolution of Secondary Alcohols: Reaction Development, Scope, and Applications

The first palladium-catalyzed enantioselective oxidation of secondary alcohols has been developed, utilizing the readily available diamine (-)-sparteine as a chiral ligand and molecular oxygen as the stoichiometric oxidant. Mechanistic insights regarding the role of the base and hydrogen-bond donors have resulted in several improvements to the original system. Namely, addition of cesium carbonate and tert-butyl alcohol greatly enhances reaction rates, promoting rapid resolutions. The use of chloroform as solvent allows the use of ambient air as the terminal oxidant at 23 °C, resulting in enhanced catalyst selectivity. These improved reaction conditions have permitted the successful kinetic resolution of benzylic, allylic, and cyclopropyl secondary alcohols to high enantiomeric excess with good-to-excellent selectivity factors. This catalyst system has also been applied to the desymmetrization of meso-diols, providing high yields of enantioenriched hydroxyketones

Magnesium(II)-ATP Complexes in 1-Ethyl-3-Methylimidazolium Acetate Solutions Characterized by 31Mg β-Radiation-Detected NMR Spectroscopy

The complexation of MgII with adenosine 5′-triphosphate (ATP) is omnipresent in biochemical energy conversion, but is difficult to interrogate directly. Here we use the spin-urn:x-wiley:14337851:media:anie202207137:anie202207137-math-0001 β-emitter 31Mg to study MgII-ATP complexation in 1-ethyl-3-methylimidazolium acetate (EMIM-Ac) solutions using β-radiation-detected nuclear magnetic resonance (β-NMR). We demonstrate that (nuclear) spin-polarized 31Mg, following ion-implantation from an accelerator beamline into EMIM-Ac, binds to ATP within its radioactive lifetime before depolarizing. The evolution of the spectra with solute concentration indicates that the implanted 31Mg initially bind to the solvent acetate anions, whereafter they undergo dynamic exchange and form either a mono- (31Mg-ATP) or di-nuclear (31MgMg-ATP) complex. The chemical shift of 31Mg-ATP is observed up-field of 31MgMg-ATP, in accord with quantum chemical calculations. These observations constitute a crucial advance towards using β-NMR to probe chemistry and biochemistry in solution

A Facile and Modular Synthesis of Phosphinooxazoline Ligands

The copper(I) iodide catalyzed phosphine/aryl halide coupling procedure of Buchwald et al. provides modular, robust, and scaleable access to phosphinooxazoline (PHOX) ligands. The advantages of this method are highlighted by the convenient synthesis of PHOX ligands with varied steric and electronic properties, which would be challenging to synthesize by other protocols

Direct measurement of the Meissner screening profile in superconductor-superconductor bilayers using low-energy muon spin rotation

Superconducting radio frequency (SRF) cavities, which are critical components in many particle accelerators, need to be operated in the Meissner state to avoid strong dissipation from magnetic vortices. For a defect-free superconductor, the maximum attainable magnetic field for operation is set by the superheating field, $B_{\mathrm{sh}}$, which directly depends on the surface current. In heterostructures composed of different superconductors, the current in each layer depends not only on the properties of the individual material, but also on the electromagnetic response of the adjacent layers through boundary conditions at the interfaces. Three prototypical bilayers [$\mathrm{Nb_{1-x}Ti_xN}$(50 nm)/Nb, $\mathrm{Nb_{1-x}Ti_xN}$(80 nm)/Nb, and $\mathrm{Nb_{1-x}Ti_xN}$(160 nm)/Nb] are investigated here by depth-resolved measurements of their Meissner screening profiles using low-energy muon spin rotation (LE-$\mu$SR). From fits to a model based on London theory (with appropriate boundary and continuity conditions), a magnetic penetration depth for the thin $\mathrm{Nb_{1-x}Ti_xN}$ layers of $\lambda_\mathrm{Nb_{1-x}Ti_xN} =$ 182.5(31) nm is found, in good agreement with literature values for the bulk alloy. In contrast, a simple London model without appropriate boundary conditions overestimates $\lambda_\mathrm{Nb_{1-x}Ti_xN}$ by more than a factor of two, suggesting that it is inappropriate for quantifying $\lambda_\mathrm{Nb_{1-x}Ti_xN}$ here. Using the measured $\lambda_\mathrm{Nb_{1-x}Ti_xN}$, the maximum vortex-free field, $B_{\mathrm{max}}$, of the superconductor-superconductor (SS) bilayer structure was estimated to be 610(40) mT. The strong suppression of the surface current in the $\mathrm{Nb_{1-x}Ti_xN}$ layer suggests an optimal thickness of $\sim 1.4 \lambda_{\mathrm{Nb_{1-x}Ti_xN}} =$ 261(14) nm.Comment: 13 pages and 8 figure

An exploration of parents’ preferences for foot care in juvenile idiopathic arthritis: a possible role for the discrete choice experiment

Background: An increased awareness of patients’ and parents’ care preferences regarding foot care is desirable from a clinical perspective as such information may be utilised to optimise care delivery. The aim of this study was to examine parents’ preferences for, and valuations of foot care and foot-related outcomes in juvenile idiopathic arthritis (JIA).<p></p> Methods: A discrete choice experiment (DCE) incorporating willingness-to-pay (WTP) questions was conducted by surveying 42 parents of children with JIA who were enrolled in a randomised-controlled trial of multidisciplinary foot care at a single UK paediatric rheumatology outpatients department. Attributes explored were: levels of pain; mobility; ability to perform activities of daily living (ADL); waiting time; referral route; and footwear. The DCE was administered at trial baseline. DCE data were analysed using a multinomial-logit-regression model to estimate preferences and relative importance of attributes of foot care. A stated-preference WTP question was presented to estimate parents’ monetary valuation of health and service improvements.<p></p> Results: Every attribute in the DCE was statistically significant (p < 0.01) except that of cost (p = 0.118), suggesting that all attributes, except cost, have an impact on parents’ preferences for foot care for their child. The magnitudes of the coefficients indicate that the strength of preference for each attribute was (in descending order): improved ability to perform ADL, reductions in foot pain, improved mobility, improved ability to wear desired footwear, multidisciplinary foot care route, and reduced waiting time. Parents’ estimated mean annual WTP for a multidisciplinary foot care service was £1,119.05.<p></p> Conclusions: In terms of foot care service provision for children with JIA, parents appear to prefer improvements in health outcomes over non-health outcomes and service process attributes. Cost was relatively less important than other attributes suggesting that it does not appear to impact on parents’ preferences.<p></p&gt

Exploring the feasibility of Conjoint Analysis as a tool for prioritizing innovations for implementation

Background: In an era of scarce and competing priorities for implementation, choosing what to implement is a key decision point for many behavioural change projects. The values and attitudes of the professionals and managers involved inevitably impact the priority attached to decision options. Reliably capturing such values is challenging. Methods: This paper presents an approach for capturing and incorporating professional values into the prioritization of healthcare innovations being considered for adoption. Conjoint Analysis (CA) was used in a single UK Primary Care Trust to measure the priorities of healthcare professionals working with women with postnatal depression. Rating-based CA data was gathered using a questionnaire and then mapped onto 12 interventions being considered as a means of improving the management of postnatal depression. Results: The ‘impact on patient care’ and the ‘quality of supporting evidence’ associated with the potential innovations were the most influential in shaping priorities. Professionals were least influenced by whether an innovation was an existing national or local priority, or whether current practice in the Trust was meeting minimum standards. Ranking the 12 innovations by the preferences of potential adopters revealed ‘guided self help’ was the top priority for implementation and ‘screening questions for post natal depression’ the least. When other factors were considered (such as the presence of routine data or planned implementation activity elsewhere in the Trust), the project team chose to combine the eight related treatments and implement these as a single innovation referred to as ‘psychological therapies’. Conclusions: Using Conjoint Analysis to prioritise potential innovation implementation options is a feasible means of capturing the utility of stakeholders and thus increasing the chances of an innovation being adopted. There are some practical barriers to overcome such as increasing response rates to conjoint surveys before routine and unevaluated use of this technique should be considered