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Research at the DReaM Facility

Read on to find out about the research recently undertaken using the Dynamic Reaction Monitoring (DReaM) Facility.

Research is undertaken at the DReaM Facility by University of Bath researchers, researchers from other academic institutions and industrialists. On this page you can explore some of the published research that has made use of the DReaM Facility.

NMR titrations in flow

"Convenient and accurate insight into solution-phase equilibria from FlowNMR titrations" has been published in Reaction Chemistry and Engineering.

FlowNMR is shown herein to be an effective technique for studying titrations. This is less labour-intensive than running individual NMR samples and the results can be obtained quickly.

Dr Dan Berry has demonstrated the technique as part of his PhD studies, with examples of Brønsted acid/base titrations (including multi-component mixtures and systems with solvent participation), hydrogen bonding interactions, Lewis acid/base interactions, and dynamic metal-ligand binding.

Diffusion NMR using flowing samples

Diffusion ordered (DOSY) NMR is an established NMR technique for obtaining information about diffusion rates and molecular size on static samples.

Dr Isabel Thomlinson has been expanding the FlowNMR toolbox to include FlowDOSY. This work has shown that if appropriate conditions are applied, such as convection compensation pulse sequences and, importantly, use of a low-pulsation pump or flow effect correction, it is possible to obtain accurate and precise diffusion coefficients at flow rates up to 4.0 mL/min - in less than 5 minutes.

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Studying catalyst behaviour in hydroformylation reactions

"Mapping catalyst activation, turnover speciation and deactivation in Rh/triphenylphosphine-catalysed olefin hydroformylation" has been published in Catalysis Science & Technology.

Further to Alejandro Bara Estaún's previous hydroformylation work, this paper reports new insights into the fate of the rhodium during hydroformylation using FlowNMR.

It was possible to characterise and quantify key intermediates formed during turnover as well as dormant dimeric carbonyl complexes. The quantitative catalyst distribution maps derived this way explain catalyst stability and activity across a range of reaction conditions, including why CO-lean conditions give faster hydroformylation catalysis.

The benefits of applying controlled temperature gradients for quantitative FlowNMR spectroscopic reaction monitoring of dynamic catalyst systems are also demonstrated.

Engineering aspects of FlowNMR spectroscopy setups

PhD students who have been undertaking work at the DReaM Facility have collaborated to review some fundamental engineering aspects of FlowNMR setups.

This will help avoid common pitfalls and work towards establishing good practice quality guidelines (GxP) for FlowNMR investigations in academia and industry. The key issues outlined in this work will be referred to in many future studies using FlowNMR setups.

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Study of polymer growth combines a continuous flow reaction with FlowNMR

"Online tracing of molecular weight evolution during radical polymerization via high-resolution FlowNMR spectroscopy" has been published in Polymer Chemistry.

Jeroen Vrijsen visited from Prof Tanja Junkers' group at Monash University and worked with Isabel Thomlinson to couple a continuous flow reactor to the NMR spectrometer in the DReaM Facility.

The researchers used diffusion ordered NMR spectroscopy to study polymer molecular weight evolution. This has advantages over other methods, such as size exclusion chromatography.

High pressure study of hydroformylation

Some of Alejandro Bara Estaún's PhD work has been published as part of the themed collection "Reaction mechanisms in catalysis".

It is challenging to study hydroformylation reactions as they occur, due to the high pressure of hydrogen and carbon monoxide used. This method has allowed the researchers to obtain knowledge of the catalytic species present.

The associated Faraday Discussion meeting took place online from the 17th to the 19th February 2021.

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New insight into ruthenium catalysis

"Insight into Catalyst Speciation and Hydrogen Co-Evolution during Enantioselective Formic Acid-driven Transfer Hydrogenation with Bifunctional Ruthenium Complexes from Multi-technique operando Reaction Monitoring" is published in Faraday Discussions.

PhD student Dan Berry has had his work published in Faraday Discussions, as part of the themed collection "Mechanistic processes in organometallic chemistry".

Simultaneous use of the NMR spectrometer, HPLC, headspace mass spectrometer and UV/Vis spectrometer yielded complementary information about the catalytic process occurring.

The Faraday Discussion meeting for this article was held in York, from the 2nd to the 4th September 2019.

Enhancing knowledge of Noyori Complexes

Dr Andrew Hall has had some of his postgraduate research published in ACS Catalysis. To study and quantify low concentrations of ruthenium hydride compounds by NMR, selective excitation experiments have been used. The researchers have showed the existence of two independent catalyst deactivation/inhibition pathways.

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FlowNMR proves useful for studying photochemical reactions

"Online monitoring of a photocatalytic reaction by real-time high resolution FlowNMR spectroscopy" has been published in Chemical Communications.

Dr Ulrich Hintermair's PhD students, Andrew Hall and Rachael Broomfield-Tagg, have worked with Matthew Camilleri and Dr David Carbery to successfully study a photocatalytic reaction via FlowNMR.

Aspects to consider when using FlowNMR

"Practical aspects of real-time reaction monitoring using multi-nuclear high resolution FlowNMR spectroscopy" has been published in Catalysis Science & Technology.

In this useful journal article, Andrew Hall's work investigates apparatus design, flow effects, acquisition parameters and data treatment and how best to set up experiments to obtain accurate kinetic data from FlowNMR spectroscopy.

Flow effects on NMR peak areas are particularly important as they can lead to large quantification errors if overlooked, but can easily be corrected for and even used to increase temporal resolution with suitably adjusted instrument settings.

The next call for proposals to use the facility will open in January 2024

Read the guidelines for use of the DReaM Facility

Contact us

If you have any questions about the research undertaken at the DReaM Facility or if you want to find out how the DReaM Facility could help with your research, please get in touch.