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We present an alternative to conventional Electron Paramagnetic Resonance (EPR) spectroscopy equipment. Avoiding the use of bulky magnets and magnetron equipment, we use the photoluminescence of an ensemble of Nitrogen-Vacancy centers at the surface of a diamond. Monitoring their relaxation time (or T1), we detected their cross-relaxation with a compound of interest. In addition, the EPR spectra are encoded through a localized magnetic field gradient. While recording previous data took 12 min per data point with individual NV centers, we were able to reconstruct a full spectrum at once in 3 s, over a range from 3 to 11 G. In terms of sensitivity, only 0.5 μL of a 1 μM hexaaquacopper(II) ion solution was necessary.

Carbon surfaces (glassy carbon, graphite, and boron-doped diamond) were functionalized with layers composed of linked pyridinium and pyridine moieties using simple electrochemical reduction of trifluoroacetylpyridinium. The pyridinium species was generated in situ in solution by the reaction of trifluoroacetic anhydride and pyridine precursors and underwent electrochemical reduction at -1.97 V vs Fc/Fc + , as determined by cyclic voltammetry. The pyridine/pyridinium films were electrodeposited at room temperature, on a timescale of minutes, and were characterized using X-ray photoelectron spectroscopy. The as-prepared films have a net positive charge in aqueous solution at pH 9 and below due to the pyridinium content, confirmed by the electrochemical response of differently charged redox molecules at the functionalized surfaces. The positive charge can be enhanced further through protonation of the neutral pyridine component by controlling the solution pH. Moreover, the nitrogen-acetyl bond can be cleaved through base treatment to purposefully increase the neutral pyridine proportion of the film. This results in a surface that can be "switched" from functionally near neutral to a positive charge by treatment in basic and acidic solutions, respectively, through manipulation of the protonation state of the pyridine. The functionalization process demonstrated here is readily achievable at a fast timescale at room temperature and hence can allow for rapid screening of surface properties. Such functionalized surfaces present a means to test in isolation the specific catalytic performance of pyridinic groups toward key processes such as oxygen and CO 2 reduction., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Copper has several biological functions, but also some toxicity, as it can act as a catalyst for oxidative damage to tissues. This is especially relevant in the presence of H 2 O 2 , a by-product of oxygen metabolism. In this study, the reactions of copper with H 2 O 2 have been investigated with spectroscopic techniques. These results were complemented by a new quantum sensing technique (relaxometry), which allows nanoscale magnetic resonance measurements at room temperature, and at nanomolar concentrations. For this purpose, we used fluorescent nanodiamonds (FNDs) containing ensembles of specific defects called nitrogen-vacancy (NV) centers. More specifically, we performed so-called T1 measurements. We use this method to provide real-time measurements of copper during a Fenton-like reaction. Unlike with other chemical fluorescent probes, we can determine both the increase and decrease in copper formed in real time.

Degradable polymers are widely used in the biomedical fields due to non-toxicity and great biocompatibility and biodegradability, and it is crucial to understand how they degrade. These polymers are exposed to various biochemical media in medical practice. Hence, it is important to precisely follow the degradation of the polymer in real time. In this study, we made use of diamond magnetometry for the first time to track polymer degradation with nanoscale precision. The method is based on a fluorescent defect in nanodiamonds, which changes its optical properties based on its magnetic surrounding. Since optical signals can be read out more sensitively than magnetic signals, this method allows unprecedented sensitivity. We used a specific mode of diamond magnetometry called relaxometry or T1 measurements. These are sensitive to magnetic noise and thus can detect paramagnetic species (gadolinium in this case). Nanodiamonds were incorporated into polylactic acid (PLA) films and PLA nanoparticles in order to follow polymer degradation. However, in principle, they can be incorporated into other polymers too. We found that T1 constants decreased gradually with the erosion of the film exposed to an alkaline condition. In addition, the mobility of nanodiamonds increased, which allows us to estimate polymer viscosity. The degradation rates obtained using this approach were in good agreement with data obtained by quartz crystal microbalance, Fourier-transform infrared spectroscopy, and atomic force microscopy.

Diamond magnetometry is a quantum sensing method involving detection of magnetic resonances with nanoscale resolution. For instance, T1 relaxation measurements, inspired by equivalent concepts in magnetic resonance imaging (MRI), provide a signal that is equivalent to T1 in conventional MRI but in a nanoscale environment. We use nanodiamonds (between 40 and 120 nm) containing ensembles of specific defects called nitrogen vacancy (NV) centers. To perform a T1 relaxation measurement, we pump the NV center in the ground state (using a laser at 532 nm) and observe how long the NV center can remain in this state. Here, we use this method to provide real-time measurements of free radicals when they are generated in a chemical reaction. Specifically, we focus on the photolysis of H 2 O 2 as well as the so-called Haber-Weiss reaction. Both of these processes are important reactions in biological environments. Unlike other fluorescent probes, diamonds are able to determine spin noise from different species in real time. We also investigate different diamond probes and their ability to sense gadolinium spin labels. Although this study was performed in a clean environment, we take into account the effects of salts and proteins that are present in a biological environment. We conduct our experiments with nanodiamonds, which are compatible with intracellular measurements. We perform measurements between 0 and 10 8 nM, and we are able to reach detection limits down to the nanomolar range and typically find T1 times of a few 100 μs. This is an important step toward label-free nano-MRI signal quantification in biological environments.

Iron centers featuring thiolates in their metal coordination sphere (as ligands or substrates) are well-known to activate dioxygen. Both heme and non-heme centers that contain iron-thiolate bonds are found in nature. Investigating the ability of iron-thiolate model complexes to activate O 2 is expected to improve the understanding of the key factors that direct reactivity to either iron or sulfur. We report here the structural and redox properties of a thiolate-based dinuclear Fe complex, [Fe II 2 (LS) 2 ] (LS 2- = 2,2'-(2,2'-bipyridine-6,6'-iyl)bis(1,1-diphenylethanethiolate)), and its reactivity with dioxygen, in comparison with its previously reported protonated counterpart, [Fe II 2 (LS)(LSH)] + . When reaction with O 2 occurs in the absence of protons or in the presence of 1 equiv of proton (i.e., from [Fe II 2 (LS)(LSH)] + ), unsupported μ-oxo or μ-hydroxo Fe III dinuclear complexes ([Fe III 2 (LS) 2 O] and [Fe III 2 (LS) 2 (OH)] + , respectively) are generated. [Fe III 2 (LS) 2 O], reported previously but isolated here for the first time from O 2 activation, is characterized by single crystal X-ray diffraction and Mössbauer, resonance Raman, and NMR spectroscopies. The addition of protons leads to the release of water and the generation of a mixture of two Fe-based "oxygen-free" species. Density functional theory calculations provide insight into the formation of the μ-oxo or μ-hydroxo Fe III dimers, suggesting that a dinuclear μ-peroxo Fe III intermediate is key to reactivity, and the structure of which changes as a function of protonation state. Compared to previously reported Mn-thiolate analogues, the evolution of the peroxo intermediates to the final products is different and involves a comproportionation vs a dismutation process for the Mn and Fe derivate, respectively.

The oxidation of the C-H and C=C bonds of hydrocarbons with H 2 O 2 catalyzed by non-heme iron complexes with pentadentate ligands is widely accepted as involving a reactive Fe IV =O species such as [(N4Py)Fe IV =O] 2+ formed by homolytic cleavage of the O-O bond of an Fe III -OOH intermediate (where N4Py is 1,1-bis(pyridin-2-yl)- N , N -bis(pyridin-2-ylmethyl)methanamine). We show here that at low H 2 O 2 concentrations the Fe IV =O species formed is detectable in methanol. Furthermore, we show that the decomposition of H 2 O 2 to water and O 2 is an important competing pathway that limits efficiency in the terminal oxidant and indeed dominates reactivity except where only sub-/near-stoichiometric amounts of H 2 O 2 are present. Although independently prepared [(N4Py)Fe IV =O] 2+ oxidizes stoichiometric H 2 O 2 rapidly, the rate of formation of Fe IV =O from the Fe III -OOH intermediate is too low to account for the rate of H 2 O 2 decomposition observed under catalytic conditions. Indeed, with excess H 2 O 2 , disproportionation to O 2 and H 2 O is due to reaction with the Fe III -OOH intermediate and thereby prevents formation of the Fe IV =O species. These data rationalize that the activity of these catalysts with respect to hydrocarbon/alkene oxidation is maximized by maintaining sub-/near-stoichiometric steady-state concentrations of H 2 O 2 , which ensure that the rate of the H 2 O 2 oxidation by the Fe III -OOH intermediate is less than the rate of the O-O bond homolysis and the subsequent reaction of the Fe IV =O species with a substrate., Competing Interests: The authors declare no competing financial interest.

The formation and spectroscopic characterization of a superoxido cobalt(iii) and a peroxido dicobalt(iii) species formed in the temperature dependent reversible reaction of a cobalt(ii) precursor with O 2 is described. The electronic nature of each species is explored in their reactivity with organic substrates.

A reactive high-valent dinuclear nickel(IV) oxido bridged complex is reported that can be formed at room temperature by reaction of [(L) 2 Ni(II) 2 (μ-X) 3 ]X (X = Cl or Br) with NaOCl in methanol or acetonitrile (where L = 1,4,7-trimethyl-1,4,7-triazacyclononane). The unusual Ni(IV) oxido species is stabilized within a dinuclear tris-μ-oxido-bridged structure as [(L) 2 Ni(IV) 2 (μ-O) 3 ] 2+ . Its structure and its reactivity with organic substrates are demonstrated through a combination of UV-vis absorption, resonance Raman, 1 H NMR, EPR, and X-ray absorption (near-edge) spectroscopy, ESI mass spectrometry, and DFT methods. The identification of a Ni(IV)-O species opens opportunities to control the reactivity of NaOCl for selective oxidations.

Terminal high-valent metal-oxygen species are key reaction intermediates in the catalytic cycle of both enzymes (e.g., oxygenases) and synthetic oxidation catalysts. While tremendous efforts have been directed toward the characterization of the biologically relevant terminal manganese-oxygen and iron-oxygen species, the corresponding analogues based on late-transition metals such as cobalt, nickel or copper are relatively scarce. This scarcity is in part related to the "Oxo Wall" concept, which predicts that late transition metals cannot support a terminal oxido ligand in a tetragonal environment. Here, the nickel(II) complex (1) of the tetradentate macrocyclic ligand bearing a 2,6-pyridinedicarboxamidate unit is shown to be an effective catalyst in the chlorination and oxidation of C-H bonds with sodium hypochlorite as terminal oxidant in the presence of acetic acid (AcOH). Insight into the active species responsible for the observed reactivity was gained through the study of the reaction of 1 with ClO - at low temperature by UV-vis absorption, resonance Raman, EPR, ESI-MS, and XAS analyses. DFT calculations aided the assignment of the trapped chromophoric species (3) as a nickel-hypochlorite species. Despite the fact that the formal oxidation state of the nickel in 3 is +4, experimental and computational analysis indicate that 3 is best formulated as a Ni III complex with one unpaired electron delocalized in the ligands surrounding the metal center. Most remarkably, 3 reacts rapidly with a range of substrates including those with strong aliphatic C-H bonds, indicating the direct involvement of 3 in the oxidation/chlorination reactions observed in the 1/ClO - /AcOH catalytic system.

The formation of an Fe(III)-OOH species by reaction of complex 1 ([(MeN3Py)Fe(II)(CH3CN)2](2+)) with H2O2 at room temperature is reported and is studied by a combination of UV/vis absorption, EPR, and resonance Raman spectroscopies. The formation of the Fe(III)-OOH species, and its subsequent conversion to relatively inert Fe(III)-O-Fe(III) species, is shown to be highly dependent on the concentration of water, with excess water favoring the formation of the latter species, which is studied by UV/vis absorption spectroelectrochemistry also. The presence of acetic acid increases the rate and extent of oxidation of 1 to its iron(III) state and inhibits the wasteful decomposition of H2O2 but does not affect significantly the spectroscopic properties of the Fe(III)-OOH species formed.

A Mn(II) complex, [Mn(dpeo)2](2+) (dpeo=1,2-di(pyridin-2-yl)ethanone oxime), activates O2, with ensuing stepwise oxidation of the methylene group in the ligands providing an alkoxide and ultimately a ketone group. X-ray crystal-structure analysis of an intermediate homoleptic alkoxide Mn(III) complex shows tridentate binding of the ligand via the two pyridyl groups and the newly installed alkoxide moiety, with the oxime group no longer coordinated. The structure of a Mn(II) complex of the final ketone ligand, cis-[MnBr2(hidpe)2] (hidpe=2-(hydroxyimino)-1,2-di(pyridine-2-yl)ethanone) shows that bidentate oxime/pyridine coordination has been resumed. H2(18)O and (18)O2 labeling experiments suggest that the inserted O atoms originate from two different O2 molecules. The progress of the oxygenation was monitored through changes in the resonance-enhanced Raman bands of the oxime unit., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Fe(III)-hypohalite complexes have been implicated in a wide range of important enzyme-catalyzed halogenation reactions including the biosynthesis of natural products and antibiotics and post-translational modification of proteins. The absence of spectroscopic data on such species precludes their identification. Herein, we report the generation and spectroscopic characterization of nonheme Fe(III)-hypohalite intermediates of possible relevance to iron halogenases. We show that Fe(III)-OCl polypyridylamine complexes can be sufficiently stable at room temperature to be characterized by UV/Vis absorption, resonance Raman and EPR spectroscopies, and cryo-ESIMS. DFT methods rationalize the pathways to the formation of the Fe(III)-OCl, and ultimately Fe(IV)=O, species and provide indirect evidence for a short-lived Fe(II)-OCl intermediate. The species observed and the pathways involved offer insight into and, importantly, a spectroscopic database for the investigation of iron halogenases., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Fe III -hypohalite complexes have been implicated in a wide range of important enzyme-catalyzed halogenation reactions including the biosynthesis of natural products and antibiotics and post-translational modification of proteins. The absence of spectroscopic data on such species precludes their identification. Herein, we report the generation and spectroscopic characterization of nonheme Fe III -hypohalite intermediates of possible relevance to iron halogenases. We show that Fe III -OCl polypyridylamine complexes can be sufficiently stable at room temperature to be characterized by UV/Vis absorption, resonance Raman and EPR spectroscopies, and cryo-ESIMS. DFT methods rationalize the pathways to the formation of the Fe III -OCl, and ultimately Fe IV =O, species and provide indirect evidence for a short-lived Fe II -OCl intermediate. The species observed and the pathways involved offer insight into and, importantly, a spectroscopic database for the investigation of iron halogenases.