Combined Electron Paramagnetic Resonance Research Articles

Synergistic photocatalysis of oxygen-enriched vacancy BiOBr based on rice husk biochar: Efficient seawater purification achieved by carrier directional migration

Addressing seawater pollution is crucial for the efficient utilization of seawater resources. Employing solar-driven seawater purification emerges as an ideal solution for the future renewable energy landscape. Herein, biomass carbon and oxygen-enriched defect materials were selected to design a high-performance photocatalyst for seawater purification. The strategic combination of defect energy levels and electron-conducting carbon enhances the directional migration and separation of photogenerated particles, thereby boosting the overall photocatalytic efficiency in seawater purification. In the simulated seawater experiment, ROV-BOB/RHC-3 exhibits significant resistant to conventional ions interference during purification. Transitioning to real seawater experiments, ROV-BOB/RHC-3 exhibits impressive removal performance for RhB and TC, achieving substantial purification in 10L of seawater under natural sunlight. Combine free radical trapping experiments and electron spin resonance (ESR) analysis shows that reactive oxygen species (•O2- and 1O2) are responsible in purification. The project provides a practical and effective basis for further research on efficient biomass carbon-based photocatalysts to seawater purification.

Activation of peroxymonosulfate with natural pyrite-biochar composite for sulfamethoxazole degradation in soil: Organic matter effects and free radical conversion

Peroxymonosulfate (PMS)-based advanced oxidation processes (AOPs) represent an effective method for the remediation of antibiotic-contaminated soils. In this study, a natural pyrite-biochar composite material (FBCx) was developed, demonstrating superior activation performance and achieving a 76% removal rate of SMX from soil within 120 min. There existed different degradation mechanisms for SMX in aqueous and soil solutions, respectively. The production of 1O2 and inherent active species produced by soil slurry played an important role in the degradation process. The combination of electron paramagnetic resonance (EPR) and free radical probe experiments confirmed the presence of free radical transformation processes in soil. Wherein, the·OH and SO4·− generated in soil slurry did not directly involve in the degradation process, but rather preferentially reacted with soil organic matter (SOM) to form alkyl-like radicals (R·), thereby maintaining a high concentration of reactive species in the system. Furthermore, germination and growth promotion of mung bean seeds observed in the toxicity test indicated the environmental compatibility of this remediation method. This study revealed the influence mechanism of SOM in the remediation process of contaminated soil comprehensively, which possessed enormous potential for application in practical environments.

Large dynamics of a phase separating arginine-glycine-rich domain revealed via nuclear and electron spins

Liquid-liquid phase separation is the key process underlying formation of membrane-less compartments in cells. A highly dynamic cellular body with rapid component exchange is Cajal body (CB), which supports the extensive compositional dynamics of the RNA splicing machinery, spliceosome. Here, we select an arginine-glycine (RG)-rich segment of coilin, the major component of CB, establish its RNA-induced phase separation, and through combined use of nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) probes, interrogate its dynamics within the crowded interior of formed droplets. Taking advantage of glycine-based singlet-states, we show that glycines retain a large level of sub-nanoseconds dynamics inside the coilin droplets. Furthermore, the continuous-wave (CW) and electron-electron dipolar (PELDOR) and electron-nucleus hyperfine coupling EPR data (HYSCORE) support the RNA-induced formation of dynamic coilin droplets with high coilin peptide concentrations. The combined NMR and EPR data reveal the high dynamics of the RG-rich coilin within droplets and suggest its potential role in the large dynamics of CBs.

Efficient piezo-photocatalysis of Bi2O2(OH)NO3/BiOI heterojunction: Collaboration of piezoelectric polarization and interface electric field

Effective removal of recalcitrant pollutants is crucial for environmental protection. Tetracycline hydrochloride, as a representative recalcitrant organic pollutant, poses a potential threat to environmental integrity when present in aquatic ecosystems. Coupling piezoelectric polarization, capable of considerably promoting the photocharge separation, acts as a very prevalent and attractive strategy to improve the photocatalytic activity. In this study, an efficient piezo-photocatalytic system was developed in Bi2O2(OH)NO3/BiOI heterojunction by collaborating with interfacial electric field and vibration-induced piezoelectric polarization. The construction of type II heterojunction allows an interfacial electric field to propel the photogenerated electrons from BiOI to Bi2O2(OH)(NO3) under visible light irradiation. The introduction of vibration-induced piezoelectric polarization field strengthens the interfacial electric field, which further promote the separation and migration of photogenerated charges. Profiting from the above advantages, Bi2O2(OH)(NO3)/BiOI heterojunction exhibited a remarkable piezo-photocatalytic performance, achieving an over 80% degradation efficiency of tetracycline hydrochloride within 10 min, which far surpasses that under individual photocatalysis or ultrasound-induced piezocatalysis and also exceeds most of the previously reported piezo-photocatalysts. The combination of electron paramagnetic resonance, piezoresponse force microscopy, COMSOL simulation, and photoelectrochemical tests are conducted to probe the synergistically-catalytic mechanism. This work not only elucidates the comprehensive impact of interfacial electric field and piezoelectric polarization on charge separation, but also highlights the tremendous potential of piezo-photocatalysis for environmental remediation.

Pyridine-bridged cobalt tetra-aminophthalocyanine to active peroxymonosulphate for efficient degrading carbamazepine

ABSTRACT In this study, each cobalt tetra-aminophthalocyanine (CoTAPc) molecule was immobilised with four isonicotinic acid (INA) molecules by amide bonding, a novel and highly efficient catalyst pyridine-bridged cobalt tetra-aminophthalocyanine (CoTAPc-TINA) was synthesised. The introduction of INA molecules promoted CoTAPc to expose more active sites, and increased the electron cloud density of cobalt ions promoting O–O bond homolysis of PMS to generate more active species, which significantly enhanced catalytic activity. With the pharmaceutical of carbamazepine (CBZ) as model pollutant, 0.1 g/L CoTAPc-TINA in dark in the presence of 0.4 mM PMS, 98.8% CBZ was removed within 10 min. However, under the same conditions the removed of CBZ was only 58.9% by CoTAPc/PMS system. Radical capture experiments combined electron paramagnetic resonance technology demonstrate that hydroxyl radicals, sulphate radicals, superoxide radicals and singlet oxygen are the main active species in the CoTAPc-TINA/PMS system. As the reaction proceeded, all aromatic intermediates were transformed to small molecular acids by these active species. This investigation provided a new insight for application of metal phthalocyanine in wastewater treatment.

Self‐Doping of the Transport Layers Decreases the Bimolecular Recombination by Reducing Static Disorder

Electron‐transport layers (ETLs) have a crucial role in the solar cells’ performance. Generally, ETLs are characterized in terms of the interface properties and conductivity rather than their effect on the photoactive layer. Herein, two ETLs, 2,9‐bis(3‐((3‐(dimethylamino)propyl)amino)propyl)anthra[2,1,9‐def:6,5,10‐d′e′f′]diisoquinoline‐1,3,8,10(2H,9H)‐tetraone (PDINN) and 2,9‐bis[3‐(dimethyloxidoamino)propyl]anthra[2,1,9‐def:6,5,10‐d′e′f′]diisoquinoline‐1,3,8,10(2H,9H)‐tetrone, are compared in the conventional PM6:Y6 organic solar cell (OSC) structure and the influence of the ETL on the photoactive layer is shown. It is shown that a significant portion of the unpaired electrons of PDINN is mobile by combining electron paramagnetic resonance and Hall effect measurements. It is established that the high doping in PDINN ETL changes the dark electron concentration of the photoactive layer. The impacts of this change in the photoactive layer can be observed in the reduced static energetic disorder, and subsequently in the (nonradiative) recombination of free carriers. The results can be used to suppress nonradiative recombination in OSC, which can significantly boost their efficiency.

Jasmine waste derived biochar as green sulfate catalysts dominate non-free radical paths efficiently degraded tetracycline

Because of the potential environmental harm caused by the extensive application of tetracycline (TC), this study used jasmine waste rich in organic matter as a precursor and one-step carbonization into metal-free carbon-based materials to efficiently activate peroxymonosulfate (PMS) toward degrading TC. The jasmine waste biochar (JWB) with a heating rate of 10 °C min−1 and a heating temperature of 700 °C was selected as the most suitable material based on its catalytic performance. The effects of catalyst dose, PMS dose, initial pH value, coexisting inorganic anions and TC concentration on the JWB/PMS/TC system were thoroughly optimized. The results showed that the degradation efficiency of TC by JWB/PMS system was 90%. Meanwhile, the combination of electron paramagnetic resonance, masking experiments and X-ray photoelectron spectrometry confirmed that JWB degraded TC mainly through the non-radical radical pathway of 1O2 oxidation and mediated the electron transfer to PMS. In addition, some degradation products were analyzed by LC-MS and possible degradation pathways of the system were proposed. Therefore, this paper proposes a novel method for recycling jasmine waste and providing a low-cost catalyst for the oxidation treatment of refractory organic matter.

Low Temperature Optical Properties of Novel Lead‐Free Cs2NaFeCl6 Perovskite Single Crystals

Lead‐free double perovskites have attracted much attention as possible alternatives to lead halide based perovskites in photovoltaic applications. However, to date only few double perovskites have been successfully employed in optoelectronic device prototypes. Therefore, the search for stable and lead‐free materials is ongoing. Here, we present the successful growth of high‐quality Cs2NaFeCl6 single crystals and their temperature‐dependent structural and optical properties. By combining electron paramagnetic resonance (EPR), crystal structure analysis and density functional theory (DFT) we could determine a cubic crystal structure with a spin of 5/2 for this material, showing strongly spin polarized character. Furthermore, combining photoluminescence (PL) and optical absorption measurements we find a bandgap of approximately 2.1 eV at room temperature as well as the presence of excitonic states. Using Elliot's formula, we are able to extract the temperature‐dependent behavior of the bandgap as well as an estimated exciton binding energy of only 20 meV at 80 K.

Dipolar NMR relaxation of adsorbates on surfaces of controlled wettability

In reservoir rocks, the term “ageing” refers to extended exposition to crude oil; a typically water-wet sandstone will then gradually become oil-wet as a consequence of the deposition of insoluble fractions of oil onto the surface grains. Rocks have been aged artificially by subjecting them to a bitumen solution at elevated temperature in order to achieve comparable surface properties for three different types of rock: Bentheimer, Berea Buff and Liège Chalk. Using saturated and aromatic model compounds as proxies for crude oil, the nuclear magnetic resonance (NMR) relaxation dispersion in native and aged rocks was compared and correlated to the properties of paramagnetic impurities in these rock types. Perfluorated liquids were found to follow the same trend as deuterated and naturally occurring oil components, suggesting they can be used as suitable tracers for wettability studies since the 19F nucleus is absent in natural sources. By combining electron paramagnetic resonance (EPR) and dynamic nuclear polarization (DNP) it becomes possible to identify and quantify the origin of the dominating relaxation processes between native and aged rocks, providing an alternative approach to assess wettability in natural rocks.

Charge Separation in BaTiO3 Nanocrystals: Spontaneous Polarization Versus Point Defect Chemistry.

The fate of photogenerated charges within ferroelectric metal oxides is key for photocatalytic applications. The authors study the contributions of i) tetragonal distortion, responsible for spontaneous polarization, and ii) point defects, on charge separation and recombination within BaTiO3 (BTO) nanocrystals of cubic and tetragonal structure. Electron paramagnetic resonance (EPR) in combination with O2 photoadsorption experiments show that BTO nanocrystals annealed at 600 °C have a charge separation yield enhanced by a factor > 10 compared to TiO2 anatase nanocrystals of similar geometries. This demonstrates for the first time the beneficial effect of the BTO perovskite nanocrystal lattice on charge separation. Strikingly, charge separation is considerably hindered within BTO nanoparticles annealed ≥ 600 °C, due to the formation of Ba-O divacancies that act as charge recombination centers. The opposing interplay between tetragonal distortion and annealing-induced defect formation inside the lattice highlights the importance of defect engineering within perovskite nanoparticles.

Radicals from tributyl phosphate decomposition: a combined electron paramagnetic resonance spectroscopic and computational chemistry investigation.

The radiation- and chemically-induced radicals from tributyl phosphate (TBP) have been characterized by EPR spectroscopy and theoretical calculations. The yield of X-ray-generated TBP radicals measured by a PBN spin trap is 0.22 μmol J-1 (2.1 radicals/100 eV) at room temperature (298 K). The EPR spectra obtained by irradiating TBP with an electron beam at 77 K are in close agreement with literature data for samples irradiated with gamma- and X-rays [https://doi.org/10.1007/BF02165504, https://doi.org/10.1016/1359-0197(89)90319-6]. Possible conformers of alkyl-type, TBP-derived radicals were analyzed by Density Functional Theory calculations. The main contribution to the experimental spectrum at 77 K is shown to be made by a conformer of the CH3˙CHCH2-radical, which contains all carbon atoms of the butyl group in the same plane. The EPR spectra of TBP radicals induced by the OH radical in aqueous solution were measured for the first time using a continuous flow system. The formation of the alkyl-type TBP radicals CH3˙CHCH2-, ˙CH2CH2-, and -CH2˙CHO- in the ratio of 5/4/1 was detected; their spectral assignment was based on quantum chemical calculations with rotational averaging of HFC constants for the corresponding beta- and alpha-protons.

Molecular interaction mechanism and structure–activity relationships of protein–polyphenol complexes revealed by side-directed spin labeling-electron paramagnetic resonance (SDSL-EPR) spectroscopy

Deciphering interactions between bioactive protein and polyphenols are critical for designing and controlling functional protein–polyphenol complexes. Herein, using the site-directed spin labeled T4 lysozyme (T4L) and rosmarinic acid (RA) as a model system, we combined electron paramagnetic resonance spectra to investigate molecular interaction mechanism of the protein–polyphenol complexes in structural or conformational details. Experimental results show that molecular interactions between T4L and RA are a process from order to disorder. TEM images display that the complexes finally assemble into quasi-spherical colloidal particles. When T4L/RA ratio is 1:1, the complexes exhibit the optimized enzymatic and antioxidant dual-functionalities due to the synergetic effect and protection mechanism. However, with excess addition of RA, the enzymatic and antioxidant activities of the complexes started to attenuate because the catalytic active site and bioactive hydroxyl groups were buried. The revealed high-resolution interaction process could help better understand the corresponding alterations between structure and functionalities.

Modeling Molecular Interactions with Wetting and Non-Wetting Rock Surfaces by Combining Electron Paramagnetic Resonance and NMR Relaxometry.

Three types of natural rocks─Bentheimer and Berea sandstones, as well as Liège Chalk─have been aged by immersion in a bitumen solution for extended periods of time in two steps, changing the surface conditions from water-wet to oil-wet. NMR relaxation dispersion measurements were carried out on water and oil constituents, with saturated and aromatic molecules considered individually. In order to separate the different relaxation mechanisms discussed in the literature, 1H and 19F relaxation times were compared to 2H for fully deuterated liquids: while 2H relaxes predominantly by quadrupolar coupling, which is an intramolecular process, the remaining nuclei relax by dipolar coupling, which potentially consists of intra- and intermolecular contributions. The wettability change becomes evident in an increase of relaxation rates for oil and a corresponding decrease for water. However, this expected behavior dominates only for the spin-lattice relaxation rate R1 at very low field strengths and for the spin-spin relaxation rate R2, while high-field longitudinal relaxation shows a much weaker or even reverse trend. This is attributed in part to a change of radical concentration on the pore surface upon coverage of the native rock surface by bitumen as well as by the change of surface chemistry and roughness. EPR and DNP measurements quantify the change of volume vs surface radical concentration in the rocks, and an improved understanding of the role of relaxation via paramagnetic centers is obtained. By means of comparing different fluids and nuclei in combination with a defined wettability change of natural rocks, a refined model for molecular dynamics in conjunction with NMR relaxation dispersion is proposed.

New chronological constraints for the lowermost stratigraphic unit of Atapuerca Gran Dolina (Burgos, N Spain)

We present the results of a combined Electron Spin Resonance (ESR) and Luminescence dating study for the lowermost stratigraphic unit (TD1) of the palaeoanthropological site of Atapuerca Gran Dolina, Spain. Ten samples collected through the Main Section were dated using either the Multiple Centre (MC) ESR approach or the single-grain thermally transferred optically stimulated luminescence (SG TT-OSL) technique, both of which were applied to quartz grains. The two methods yield consistent ages, providing a robust chronostratigraphic framework for the TD1 deposits and enabling improved correlation of the magnetostratigraphic succession (comprising three intervals of normal polarity; N1 to N3, from bottom to top) with the Geomagnetic Polarity Time Scale. Specifically, the results provide a late Early Pleistocene chronology for TD1, and clearly position the deposits in the post-Olduvai time range (<1.77 Ma). The final age estimates range from 1.30 ± 0.14 Ma (TT-OSL) close to the bottom of the section to a mean ESR age of 1.05 ± 0.12 Ma (1 s.d.) for three samples from the N3 interval towards the top. Consequently, the N3 interval may confidently be correlated to the Jaramillo Subchron, while we propose a correlation of N1 and N2 with the Cobb Mountain subchron and Punaruu excursion, respectively; although we cannot exclude that these two normal intervals may correspond to other, unknown, geomagnetic events given the existing uncertainties associated with the ESR and luminescence ages. From a methodological point of view, the ESR MC approach shows that the Titanium signal provides the most reliable burial ages for TD1. In contrast, the Aluminium centre yields systematically overestimated age estimates, as a result of incomplete resetting of the signal before sediment deposition. The SG TT-OSL ages presented here are amongst the oldest published so far, and highlight the potential of the high temperature SG TT-OSL 290 approach for obtaining finite ages exceeding 1 Ma at Atapuerca. Finally, these new dating results provide key insights into the rates and nature of sedimentary processes at Gran Dolina, modifying long-standing interpretations of the cave formation and infilling dynamics. An age of at least 1.4 Ma may be inferred for the base of the sedimentary infill at the Main Section, providing minimum age constraint for the formation of the cavity and, by extension, for the intermediate level of the Atapuerca karst. The opening of the cave, which pre-dates human occupation, most likely occurred close to or slightly after 0.9 Ma. This suggests that both TD4 and TD6 archaeological levels were deposited within a relatively short time range of <100 kyr. The so-called autochthonous fluvial deposits from TD1 unit, or at least those dated in the present study, were also clearly primarily derived from outside the karst system, and were not reworked from older deposits within the karst. They experienced sufficient daylight exposure and minimum transport times within the karst system to enable consistency between the ESR and TT-OSL burial ages and the independent magnetostratigraphic evidence. Our results highlight the need to reconsider the terminology traditionally employed to differentiate the two main phases of Gran Dolina's sedimentary infill. New numerical age results for stratigraphic unit TD1 of Atapuerca Gran Dolina, Spain The presence of Jaramillo magnetic Subchron (1.07-0.99 Ma) is confirmed The base of the sedimentary infill post-dates Oduvai Subchron (<1.77 Ma) Cave opening occurred ca. 0.9 Ma ago, suggesting that TD4-6 units deposited in < 100 kyr TD1 fluvial deposits do not originate from within the karst

Formation of free radicals in human hair under strain: Combined electron paramagnetic resonance (EPR) – Strain technique

In this work, the formation of free radicals in human hair and the evolution of the radical concentration under strain, using a combined electron paramagnetic resonance (EPR) – strain technique, has been investigated. The radicals formed in the hair as a result of homolytic bond cleavage in cystine residues of polypeptide chains were identified. Stability of the radicals formed in dry hair and in the presence of water were studied. The spin–strain curves for the grey human hair in dry state and in water are presented and compared with conventional hair stress vs. strain curves. The evolution of sulfur radical species has been found to only occur at strains of above ca. 25%, corresponding with the Post-Yield region of the stress vs. strain behaviour for hair; this indicates that the matrix of the hair in this region behaves like a highly crosslinked gel and helps to explain the reversibility in hair mechanical behaviour below the Post-Yield region.

Electron Paramagnetic Resonance of Alkali Metal Atoms and Dimers on Ultrathin MgO.

Electron paramagnetic resonance (EPR) can provide unique insight into the chemical structure and magnetic properties of dopants in oxide and semiconducting materials that are of interest for applications in electronics, catalysis, and quantum sensing. Here, we demonstrate that EPR in combination with scanning tunneling microscopy (STM) allows for probing the bonding and charge state of alkali metal atoms on an ultrathin magnesium oxide layer on a Ag substrate. We observe a magnetic moment of 1 μB for Li2, LiNa, and Na2 dimers corresponding to spin radicals with a charge state of +1e. Single alkali atoms have the same charge state and no magnetic moment. The ionization of the adsorbates is attributed to charge transfer through the oxide to the metal substrate. Our work highlights the potential of EPR-STM to provide insight into dopant atoms that are relevant for the control of the electrical properties of surfaces and nanodevices.

Molecular insights into the role of heme in the transcriptional regulatory system AppA/PpsR

Heme has been shown to have a crucial role in the signal transduction mechanism of the facultative photoheterotrophic bacterium Rhodobacter sphaeroides. It interacts with the transcriptional regulatory complex AppA/PpsR, in which AppA and PpsR function as the antirepressor and repressor, respectively, of photosynthesis gene expression. The mechanism, however, of this interaction remains incompletely understood. In this study, we combined electron paramagnetic resonance (EPR) spectroscopy and Förster resonance energy transfer (FRET) to demonstrate the ligation of heme in PpsR with a proposed cysteine residue. We show that heme binding in AppA affects the fluorescent properties of the dark-adapted state of the protein, suggesting a less constrained flavin environment compared with the absence of heme and the light-adapted state. We performed ultrafast transient absorption measurements in order to reveal potential differences in the dynamic processes in the full-length AppA and its heme-binding domain alone. Comparison of the CO-binding dynamics demonstrates a more open heme pocket in the holo-protein, qualitatively similar to what has been observed in the CO sensor RcoM-2, and suggests a communication path between the blue-light-using flavin (BLUF) and sensing containing heme instead of cobalamin (SCHIC) domains of AppA. We have also examined quantitatively the affinity of PpsR to bind to individual DNA fragments of the puc promoter using fluorescence anisotropy assays. We conclude that oligomerization of PpsR is initially triggered by binding of one of the two DNA fragments and observe a ∼10-fold increase in the dissociation constant Kd for DNA binding upon heme binding to PpsR. Our study provides significant new insight at the molecular level on the regulatory role of heme that modulates the complex transcriptional regulation in R. sphaeroides and supports the two levels of heme signaling, via its binding to AppA and PpsR and via the sensing of gases like oxygen.

Maximizing the applicability of continuous wave (CW) Electron Paramagnetic Resonance (EPR): what more can we do after a century?

Electron Paramagnetic Resonance/Electron Spin Resonance (EPR/ESR) spectroscopy is a powerful experimental approach solving challenging problems that are inaccessible to other experimental techniques. While pulsed EPR techniques and their applications have been the central focus of the field nowadays, methodology development and application of continuous wave (CW) EPR have never been undervalued. Although the importance of EPR in research has been recognized in many areas as indicated by the increasing number of EPR research articles published every year, the growth in the number of EPR research teams seems to not match the former, likely caused by the relatively high cost of modern pulsed EPR spectrometers. In this perspective, we aim to discuss the new areas and new directions of the application of CW EPR in combination with spin labeling that are slightly different from the classic/traditional applications of the CW EPR technique. Based on our experience, we show example applications of CW EPR on the interfaces of protein-confinement materials, protein-inorganic crystal lattices, protein-nanoparticles, and protein-polymers. Various structure and dynamics information can be resolved from the data analysis of CW EPR, leading to enhanced understanding of protein biophysics upon interaction with the synthetic nanostructures as well as possible guidance of hybrid materials development based on the combination of proteins and nanostructures. We also discussed the possibilities of even broadening the application spectrum of EPR spectroscopy. The relatively high affordability of CW EPR spectrometers (as compared to the pulsed ones) also facilitates the growth in EPR research groups worldwide.

Intermolecular interactions of tetracyanoethylene (TCNE) and fumaronitrile (FN) with minor amines: A combined UV-Vis and EPR study.

In this paper, the nature of interactions between two cyanocarbons-tetracyanoethylene (TCNE) and fumaronitrile (FN)-and a series of four secondary amines possessing a general formula C4HxN (x = 5-11) is thoroughly scrutinized. For all of the TCNE-amine pairs, tricyanovinylation (TCV) reaction is observed; however, only for pyrrole, it is accompanied with a visible charge-transfer (CT) complex formation-no such chemical individuals, characteristic for TCNE, have been noticed for aliphatic and alicyclic amines. On the contrary, FN forms such complexes with all the amines studied. Interestingly, a rather unexpected reaction of FN with alicyclic amines has been observed. The recorded electron paramagnetic resonance (EPR) spectra indicate the presence of both TCNE●- and FN●- radicals in the analyzed samples, assigned to a complete charge (electron) transfer process within the CT complexes, whose efficiency can be additionally enhanced by photoirradiation. The origination of the former radical, whose presence is observed also in the TCNE-diethylamine mixture, is as well proposed to result indirectly from the TCV reaction, occurring for this system. Finally, the superhyperfine structure of EPR spectra, indicating the existence of some secondary interactions of the radicals with surrounding compounds, is discussed. Formation of CT complexes and tricyanovinylates has been investigated and characterized with UV-Vis spectroscopy, while the presence of (cyano)radicals in the analyzed mixtures has been evidenced by (photoinduced) EPR measurements. Interpretation of the experimental results is also supplemented with computer simulations including density functional theory calculations.

Crystallographic snapshots of a B12-dependent radical SAM methyltransferase

By catalysing the microbial formation of methane, methyl-coenzyme M reductase has a central role in the global levels of this greenhouse gas1,2. The activity of methyl-coenzyme M reductase is profoundly affected by several unique post-translational modifications3–6, such as a unique C-methylation reaction catalysed by methanogenesis marker protein 10 (Mmp10), a radical S-adenosyl-l-methionine (SAM) enzyme7,8. Here we report the spectroscopic investigation and atomic resolution structure of Mmp10 from Methanosarcina acetivorans, a unique B12 (cobalamin)-dependent radical SAM enzyme9. The structure of Mmp10 reveals a unique enzyme architecture with four metallic centres and critical structural features involved in the control of catalysis. In addition, the structure of the enzyme–substrate complex offers a glimpse into a B12-dependent radical SAM enzyme in a precatalytic state. By combining electron paramagnetic resonance spectroscopy, structural biology and biochemistry, our study illuminates the mechanism by which the emerging superfamily of B12-dependent radical SAM enzymes catalyse chemically challenging alkylation reactions and identifies distinctive active site rearrangements to provide a structural rationale for the dual use of the SAM cofactor for radical and nucleophilic chemistry.