Publications
If the results of the measurements performed at the PEPR Facility are included in a publication, the following statement shall be added to the Acknowledgments section: "The EPR measurements were performed at the Centre for Pulse EPR at Imperial College London (PEPR), supported by the EPSRC grant EP/T031425/1."
We would be grateful if the Facility could be informed of the submission by sending an e-mail to m.roessler@imperial.ac.uk and a.collauto@imperial.ac.uk.
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Journal articleStadler B, Meng HHY, Belazregue S, et al., 2023,
PCP Pincer Complexes of Titanium in the+3 and+4 Oxidation States
, ORGANOMETALLICS, Vol: 42, Pages: 1278-1285, ISSN: 0276-7333- Author Web Link
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- Citations: 1
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Journal articlePichler CM, Bhattacharjee S, Lam E, et al., 2022,
Bio-electrocatalytic conversion of food waste to ethylene via succinic acid as the central intermediate
, ACS Catalysis, Vol: 12, Pages: 13360-13371, ISSN: 2155-5435Ethylene is an important feedstock in the chemical industry, but currently requires production from fossil resources. The electrocatalytic oxidative decarboxylation of succinic acid offers in principle an environmentally friendly route to generate ethylene. Here, a detailed investigation of the role of different carbon electrode materials and characteristics revealed that a flat electrode surface and high ordering of the carbon material are conducive for the reaction. A range of electrochemical and spectroscopic approaches such as Koutecky–Levich analysis, rotating ring-disk electrode (RRDE) studies, and Tafel analysis as well as quantum chemical calculations, electron paramagnetic resonance (EPR), and in situ infrared (IR) spectroscopy generated further insights into the mechanism of the overall process. A distinct reaction intermediate was detected, and the decarboxylation onset potential was determined to be 2.2–2.3 V versus the reversible hydrogen electrode (RHE). Following the mechanistic studies and electrode optimization, a two-step bio-electrochemical process was established for ethylene production using succinic acid sourced from food waste. The initial step of this integrated process involves microbial hydrolysis/fermentation of food waste into aqueous solutions containing succinic acid (0.3 M; 3.75 mmol per g bakery waste). The second step is the electro-oxidation of the obtained intermediate succinic acid to ethylene using a flow setup at room temperature, with a productivity of 0.4–1 μmol ethylene cmelectrode–2 h–1. This approach provides an alternative strategy to produce ethylene from food waste under ambient conditions using renewable energy.
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Journal articleRichardson K, Wright JJ, Simenas M, et al., 2021,
Functional basis of electron transport within photosynthetic complex I
, Nature Communications, Vol: 12, Pages: 1-8, ISSN: 2041-1723Photosynthesis and respiration rely upon a proton gradient to produce ATP. In photosynthesis, the Respiratory Complex I homologue, Photosynthetic Complex I (PS-CI) is proposed to couple ferredoxin oxidation and plastoquinone reduction to proton pumping across thylakoid membranes. However, little is known about the PS-CI molecular mechanism and attempts to understand its function have previously been frustrated by its large size and high lability. Here, we overcome these challenges by pushing the limits in sample size and spectroscopic sensitivity, to determine arguably the most important property of any electron transport enzyme – the reduction potentials of its cofactors, in this case the iron-sulphur clusters of PS-CI (N0, N1 and N2), and unambiguously assign them to the structure using double electron-electron resonance. We have thus determined the bioenergetics of the electron transfer relay and provide insight into the mechanism of PS-CI, laying the foundations for understanding of how this important bioenergetic complex functions.
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Journal articleRimmele M, Nogala W, Seif-Eddine M, et al., 2021,
Functional group introduction and aromatic unit variation in a set of π‑conjugated macrocycles: revealing the central role of local and global aromaticity
, Organic Chemistry Frontiers, Vol: 8, Pages: 4730-4745, ISSN: 2052-4110π-Conjugated macrocycles are molecules with unique properties that are increasingly exploited for applications and the question of whether they can sustain global aromatic or antiaromatic ring currents is particularly intriguing. However, there are only a small number of experimental studies that investigate how the properties of π‑conjugated macrocycles evolve with systematic structural changes. Here, we present such a systematic experimental study of a set of [2.2.2.2]cyclophanetetraenes, all with formally Hückel antiaromatic ground states, and combine it with an in-depth computational analysis. The study reveals the central role of local and global aromaticity for rationalizing the observed optoelectronic properties, ranging from extremely large Stokes shifts of up to 1.6 eV to reversible fourfold reduction, a highly useful feature for charge storage/accumulation applications. A recently developed method for the visualization of chemical shielding tensors (VIST) is applied to provide unique insight into local and global ring currents occurring in different planes along the macrocycle. Conformational changes as a result of the structural variations can further explain some of the observations. The study contributes to the development of structure–property relationships and molecular design guidelines and will help to understand, rationalize, and predict the properties of other π‑conjugated macrocycles.
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Journal articleHameedi MA, Grba DN, Richardson KH, et al., 2021,
A conserved arginine residue is critical for stabilizing the N2 FeS cluster in mitochondrial complex I
, Journal of Biological Chemistry, Vol: 296, ISSN: 0021-9258Respiratory complex I (NADH:ubiquinone oxidoreductase), the first enzyme of the electron-transport chain, captures the free energy released by NADH oxidation and ubiquinone reduction to translocate protons across an energy-transducing membrane and drive ATP synthesis during oxidative phosphorylation. The cofactor that transfers the electrons directly to ubiquinone is an iron-sulfur cluster (N2) located in the NDUFS2/NUCM subunit. A nearby arginine residue (R121), which forms part of the second coordination sphere of the N2 cluster, is known to be post-translationally dimethylated but its functional and structural significance are not known. Here, we show that mutations of this arginine residue (R121M/K) abolish the quinone-reductase activity, concomitant with disappearance of the N2 signature from the electron paramagnetic resonance (EPR) spectrum. Analysis of the cryo-EM structure of NDUFS2-R121M complex I at 3.7 Å resolution identified the absence of the cubane N2 cluster as the cause of the dysfunction, within an otherwise intact enzyme. The mutation further induced localised disorder in nearby elements of the quinone-binding site, consistent with the close connections between the cluster and substrate-binding regions. Our results demonstrate that R121 is required for the formation and/or stability of the N2 cluster, and highlight the importance of structural analyses for mechanistic interpretation of biochemical and spectroscopic data on complex I variants.
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Journal articleŠimėnas M, OSullivan J, Zollitsch CW, et al., 2021,
A sensitivity leap for X-band EPR using a probehead with a cryogenic preamplifier
, Journal of Magnetic Resonance, Vol: 322, Pages: 1-7, ISSN: 1090-7807Inspired by the considerable success of cryogenically cooled NMR cryoprobes, we present an upgraded X-band EPR probehead, equipped with a cryogenic low-noise preamplifier. Our setup suppresses source noise, can handle the high microwave powers typical in X-band pulsed EPR, and is compatible with the convenient resonator coupling and sample access found on commercially available spectrometers. Our approach allows standard pulsed and continuous-wave EPR experiments to be performed at X-band frequency with significantly increased sensitivity compared to the unmodified setup. The probehead demonstrates a voltage signal-to-noise ratio (SNR) enhancement by a factor close to 8× at a temperature of 6 K, and remains close to 2× at room temperature. By further suppressing room-temperature noise at the expense of reduced microwave power (and thus minimum -pulse length), the factor of SNR improvement approaches 15 at 6 K, corresponding to an impressive 200-fold reduction in EPR measurement time. We reveal the full potential of this probehead by demonstrating such SNR improvements using a suite of typical hyperfine and dipolar spectroscopy experiments on exemplary samples.
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Journal articleBajada MA, Roy S, Warnan J, et al., 2020,
A Precious-Metal-Free Hybrid Electrolyzer for Alcohol Oxidation Coupled to CO<inf>2</inf>-to-Syngas Conversion
, Angewandte Chemie, Vol: 132, Pages: 15763-15771, ISSN: 0044-8249© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA Electrolyzers combining CO2 reduction (CO2R) with organic substrate oxidation can produce fuel and chemical feedstocks with a relatively low energy requirement when compared to systems that source electrons from water oxidation. Here, we report an anodic hybrid assembly based on a (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) electrocatalyst modified with a silatrane-anchor (STEMPO), which is covalently immobilized on a mesoporous indium tin oxide (mesoITO) scaffold for efficient alcohol oxidation (AlcOx). This molecular anode was subsequently combined with a cathode consisting of a polymeric cobalt phthalocyanine on carbon nanotubes to construct a hybrid, precious-metal-free coupled AlcOx–CO2R electrolyzer. After three-hour electrolysis, glycerol is selectively oxidized to glyceraldehyde with a turnover number (TON) of ≈1000 and Faradaic efficiency (FE) of 83 %. The cathode generated a stoichiometric amount of syngas with a CO:H2 ratio of 1.25±0.25 and an overall cobalt-based TON of 894 with a FE of 82 %. This prototype device inspires the design and implementation of nonconventional strategies for coupling CO2R to less energy demanding, and value-added, oxidative chemistry.
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