Multi-nuclear, high-pressure, operando FlowNMR spectroscopic study of Rh/PPh3 – catalysed hydroformylation of 1-hexene

The hydroformylation of 1-hexene with 12 bar of 1 : 1 H2/CO in the presence of the catalytic system [Rh(acac)(CO)2]/PPh3 was successfully studied by real-time multinuclear high-resolution FlowNMR spectroscopy at 50 °C. Quantitative reaction progress curves that yield rates as well as chemo- and regioselectivities have been obtained with varying P/Rh loadings. Dissolved H2 can be monitored in solution to ensure true operando conditions without gas limitation. 31P{1H} and selective excitation 1H pulse sequences have been periodically interleaved with 1H FlowNMR measurements to detect Rh–phosphine intermediates during the catalysis. Stopped-flow experiments in combination with diffusion measurements and 2D heteronuclear correlation experiments showed the known tris-phosphine complex [RhH(CO)(PPh3)3] to generate rapidly exchanging isomers of the bis-phosphine complex [Rh(CO)2(PPh3)2] under CO pressure that directly enter the catalytic cycle. A new mono-phosphine acyl complex has been identified as an in-cycle reaction intermediate

Metal triflates for the production of aromatics from lignin

This work was funded by the European Union (Marie Curie ITN ‘SuBiCat’ PITN-GA-2013-607044, PJD, CWL, NJW, PCKL, KB, JGdeV) as well as EP/J018139/1, EP/K00445X/1 grants (NJW and PCJK) and an EPSRC Doctoral Prize Fellowship (CSL).The depolymerization of lignin into valuable aromatic chemicals is one of the key goals towards establishing economically viable biorefineries. In this contribution we present a simple approach for converting lignin to aromatic monomers in high yields, under mild reaction conditions. The methodology relies on the use of catalytic amounts of easy to handle metal triflates (M(OTf)x). Initially, we evaluated the reactivity of a broad range of metal triflates using simple lignin model compounds. More advanced lignin model compounds were also used to study the reactivity of different lignin linkages. The product aromatic monomers were either phenolic C2-acetals obtained by stabilization of the aldehyde cleavage products by reaction with ethylene glycol, or methyl aromatics obtained by catalytic decarbonylation. Notably, when the former method was ultimately tested on lignin, especially Fe(OTf)3 proved very effective and the phenolic C2-acetal products were obtained in an excellent, 19.3±3.2 wt % yield.PostprintPeer reviewe

Assessing the efficacy and cost of detergents used in a primary care automated washer disinfector

Background: Cleaning of re-usable medical devices is a critical control point in the decontamination cycle, although defined end-points of the process are controversial. Objective: Investigate cleaning efficacy and cost of different detergent classes in an automated washer disinfector (AWD) designed for dental practice. Methods: Loads comprised test soiled dental hand instruments in cassettes and extraction forceps. Residual protein assayed using the International standard method (ISO 15883-5:2005) 1% SDS elution with ortho-phthalaldehyde (OPA) or GBox technology (on instrument OPA analysis). Short (60 minutes) and long (97 minutes) AWD cycles were used with four different classes of detergents, tap water and reverse osmosis water. Results: SDS elution analysis (N = 612 instruments) demonstrated four detergents with both wash cycles achieved equivalent cleanliness levels and below a threshold of 200 μg protein/instrument. GBox methodology (N = 575) using UK Department of Health threshold of 5 μg/instrument side demonstrated that tap water performed with the greatest efficacy for all types of instruments and cycle types. Conclusions: Using International standard methodology, different detergent classes had equivalence in cleaning efficacy. Cheaper detergents used in this study performed with similar efficacy to more expensive solutions. Findings emphasise the importance of validating the detergent (type and concentration) for each AWD

Artificial Metalloenzymes as Catalysts for Oxidative Lignin Degradation

We report novel artificial metalloenzymes (ArMs), containing tris­(pyridylmethyl)­amine (TPA), for the atom economic oxidation of lignin β-O-4 model compounds, using hydrogen peroxide. The protein scaffold alters the selectivity of the reaction from a low yielding cleavage reaction when using the parent Fe-tpa complex to a high yielding benzylic alcohol oxidation when using the complex incorporated into a protein scaffold, SCP-2L A100C. Engineering the protein scaffold to incorporate glutamic acid was found to improve the ArM activity, showing that rational design of the protein environment using metal binding amino acids can be a first step toward improving the overall activity of an artificial metalloenzyme