No abstract

The kinetics and mechanism of the base-catalyzed hydrolysis (ArB(OR) 2 → ArB(OH) 2 ) and protodeboronation (ArB(OR) 2 → ArH) of a series of boronic esters, encompassing eight different polyols and 10 polyfluoroaryl and heteroaryl moieties, have been investigated by in situ and stopped-flow NMR spectroscopy ( 19 F, 1 H, and 11 B), pH-rate dependence, isotope entrainment, 2 H KIEs, and KS-DFT computations. The study reveals the phenomenological stability of boronic esters under basic aqueous−organic conditions to be highly nuanced. In contrast to common assumption, esterification does not necessarily impart greater stability compared to the corresponding boronic acid. Moreover, hydrolysis of the ester to the boronic acid can be a dominant component of the overall protodeboronation process, augmented by self-, auto-, and oxidative (phenolic) catalysis when the pH is close to the pK a of the boronic acid/ester.

Abstract:The hazardous diazo transfer reagent mesyl azide has been safely generated and used in situ for continuous diazo transfer as part of an integrated synthetic process with an embedded safety quench. Diazo transfer to -keto esters and a -

Background Stroke Survivors (SSs) often present with an increased fall risk due to physical, sensory, cognitive and visual impairments. Footwear has the potential to positively impact the gait and balance of SSs, while poorly fitting or unsupportive footwear is associated with falls. Research to date has focused on older adult populations. Little is known about the type of footwear SSs wear on an Acute Stroke Unit (ASU). The aim of this study was to identify the type and suitability of footwear available to SSs on an ASU. Methods Consecutive inpatients (>18) on a 31-bed ASU were assessed on one day in May 2022. Footwear available to SSs was assessed for suitability using the Footwear Assessment Tool, a six-item tool with established inter- and intra-rater reliability. Descriptive statistics were employed to examine results. Results In all, 38 pairs of footwear were available to 31 patients with a median age of 72 and 61% (19/31) were male. Two or more types of footwear were available to 29% (9/31) of patients, 61% (19/31) had one type of footwear available, while 10% (3/31) had no footwear. The most common type of footwear were slippers with backs (36%; 14/38) followed by athletic shoes (21%; 8/31) and backless slippers were the last common type (3%; 1/38). Based on the Footwear Assessment Tool, less than half (47%; 18/38) of the footwear available were appropriate. Conclusion This study highlights the large number of SSs in an ASU who have inappropriate footwear to support their rehabilitation and safety. Ensuring SSs have suitable footwear is a simple way of promoting safety and improving mobility. Healthcare professions have a responsibility to consider footwear characteristics in the management of SSs. Evidence-based advice to patients and families on safe and appropriate footwear could improve rehabilitation outcomes while minimising falls risk.