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.
"Controlled Amine-Borane Dehydropolymerization Enabled by Mechanistic Insight Using the Ir(tBu-POCOP)H2 Catalyst" has been published in the Journal of the American Chemical Society.
Dr Chloe van Beek, under the PhD supervision of Prof Andrew Weller, has undertaken a detailed kinetic, mechanistic, and operando speciation study, which benefited from the flowNMR capabilities in the DReaM Facility.
This research adds to previous research from the group, creating a variety of well-studied catalysts for dehydropolymerization to make polyaminoboranes.
"Catalyst speciation and deactivation in the ruthenium-mediated transformation of ethynyl-β-ionol to α,β-unsaturated esters for vitamin A synthesis" has been published in Catalysis Science & Technology.
Dr Asad Saib's PhD work with Dr Uli Hintermair focused on use of multi-nuclear high resolution flowNMR spectroscopy to understand the stability of ruthenium catalysts. These catalysts are used in one of the steps in the synthesis of vitamin A.
Optimising the conditions that the catalysts operate in enabled Asad to increase the productivity of the catalyst, and these optimised conditions may be applicable to other catalysts and substrates.
Dr Alejandro Bara Estaún and Marie Harder have had some of their research published in Chemistry-A European Journal. To study and quantify low concentrations of compounds by NMR, paramagnetic relaxation agents have been used. The researchers have shown which agents are stable under harsh conditions, and demonstrated a substantial increase in data quality.
Read the article"Understanding Rh-catalysed Hydroformylation with Phosphite Ligands through Catalyst Speciation Analysis by Operando FlowNMR Spectroscopy" is published in ChemCatChem.
Dr Alejandro Bara Estaún has had his research published in ChemCatChem, expanding the range of ligands he has studied using flowNMR to include phosphites.
Phosphites are important ligands in industrial processes. Alejandro's work helps to explain why phosphites contribute to more active catalysts, and provides information to enable future researchers in the field to compare types of ligands, which will allow them to choose the most appropriate type for their reactions.
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.
Read the article"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.
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.
Read the article"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.
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.
Read the article"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.
Please find some of our older research articles linked below.
The next call for proposals to use the facility will open at the end of January 2027
Read the guidelines for use of the DReaM FacilityIf 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.
