Preparation of difluoromethylthioethers through difluoromethylation of disulfides using TMS-CF2H

We report an operationally simple, metal-free approach for the late-stage introduction of the important lipophilic hydrogen-bond donor motif, SCF2H. This reaction converts diaryl- and dialkyl-disulfides into the corresponding aryl/alkyl–SCF2H through the nucleophilic transfer of a difluoromethyl group with good functional group tolerance. This method is notable for its use of commercially available TMSCF2H, and does not rely on the need for handling of sensitive metal complexes

Continuous Flow Metathesis for Direct Valorization of Food Waste: An Example of Cocoa Butter Triglyceride.

The direct chemical conversion of cocoa butter triglycerides, a material available as a postmanufacture waste stream from the food industry, to 1-decene by way of ethenolysis is reported. The conversion of the raw waste material was made possible by use of 1 mol % of the [RuCl2(iBu-phoban)2(3-phenylindenyl)] catalyst. The process has been investigated in both batch and flow conditions, where the latter approach employs a Teflon AF-2400 tube-in-tube gas-liquid membrane contactor to deliver ethylene to the reaction system. These preliminary studies culminate in a continuous processing system, which maintained a constant output over a 150 min period tested.The ERC (Advanced Investigator Award-FUNCAT to S.P.N.) and EPSRC are gratefully acknowledged for support (S.V.L., D.L.B., Award No. EP/K009494/1). Umicore AG is acknowledged for their generous gift of materials. S.P.N. is a Royal Society Wolfson Research Merit Award holder.This is the final version of the article. It first appeared from ACS via http://dx.doi.org/10.1021/acssuschemeng.5b00397

Continuous Flow Metathesis for Direct Valorization of Food Waste: An Example of Cocoa Butter Triglyceride.

The direct chemical conversion of cocoa butter triglycerides, a material available as a postmanufacture waste stream from the food industry, to 1-decene by way of ethenolysis is reported. The conversion of the raw waste material was made possible by use of 1 mol % of the [RuCl2(iBu-phoban)2(3-phenylindenyl)] catalyst. The process has been investigated in both batch and flow conditions, where the latter approach employs a Teflon AF-2400 tube-in-tube gas-liquid membrane contactor to deliver ethylene to the reaction system. These preliminary studies culminate in a continuous processing system, which maintained a constant output over a 150 min period tested.The ERC (Advanced Investigator Award-FUNCAT to S.P.N.) and EPSRC are gratefully acknowledged for support (S.V.L., D.L.B., Award No. EP/K009494/1). Umicore AG is acknowledged for their generous gift of materials. S.P.N. is a Royal Society Wolfson Research Merit Award holder.This is the final version of the article. It first appeared from ACS via http://dx.doi.org/10.1021/acssuschemeng.5b00397

Data set for the use of alternating polarity in synthetic chemistry

This is the affiliated data set for the publication “Alternating polarity for enhanced electrochemical synthesis” including all raw and processed data used in this study

Latent class analysis identifies functional decline with Amsterdam IADL in preclinical Alzheimer's disease

Introduction: Trials in Alzheimer's disease (AD) now include participants at the earliest stages to prevent further decline. However, the lack of tools sensitive to subtle functional changes in early-stage AD hinders the development of new therapies as it is difficult to prove their clinical relevance. Methods: We assessed functional changes over three years in 289 elderly memory complainers from the Investigation of Alzheimer's Predictors in subjective memory complainers cohort using the Amsterdam Instrumental-Activities-of-Daily-Living questionnaire (A-IADL-Q). Results: No overall functional decline related to AD imaging markers was evidenced. However, five distinct classes of A-IADL-Q trajectories were identified. The largest class (212 [73.4%]) had stable A-IADL-Q scores over 3 years. A second group (23 [8.0%]) showed a persistent functional decline, higher amyloid load (P =.0005), and lower education (P =.0392). Discussion: The A-IADL-Q identified a subtle functional decline in asymptomatic at-risk AD individuals. This could have important implications in the field of early intervention in AD

Cortical amyloid accumulation is associated with alterations of structural integrity in older people with subjective memory complaints

International audienceWe determined the effect of cortical amyloid load using 18F-florbetapir PET on cognitive performance and gray matter structural integrity derived from MRI in 318 cognitively normally performing older people with subjective memory impairment from the INSIGHT-preAD cohort using multivariate partial least squares regression. Amyloid uptake was associated with reduced gray matter structural integrity in hippocampus, entorhinal and cingulate cortex, middle temporal gyrus, prefrontal cortex, and lentiform nucleus (p < 0.01, permutation test). Higher amyloid load was associated with poorer global cognitive performance, delayed recall and attention (p < 0.05), independently of its effects on gray matter connectivity. These findings agree with the assumption of a two-stage effect of amyloid on cognition, (1) an early direct effect in the preclinical stages of Alzheimer's disease and (2) a delayed effect mediated by downstream effects of amyloid accumulation, such as gray matter connectivity decline

A continuous flow-batch hybrid reactor for commodity chemical synthesis enabled by inline NMR and temperature monitoring

Inline, real time NMR and temperature measurements have been used to optimise the continuous flow synthesis of difluoromethyltrimethylsilane (TMSCF2H) by the reduction of the Ruppert-Prakash reagent (TMSCF3). These measurements were used to maximise the space-time-yield, while ensuring this exothermic process remains safe. In this way, a three-fold increase in space-time-yield was achieved compared to the reported batch procedure, isolating 25 g of pure TMSCF2H after 105 min