Nitrogen-vacancy (NV) centers in millimeter-scale diamond samples were produced by irradiation and subsequent annealing under varied conditions. The optical and spin relaxation properties of these samples were characterized using confocal microscopy, visible and infrared absorption, and optically detected magnetic resonance. The sample with the highest NV concentration, approximately 16 ppm (2.8 × 10 18 cm −3 ), was prepared with no observable traces of neutrally-charged vacancy defects. The eective transverse spin-relaxation time for this sample was T * 2 = 118(48) ns, predominately limited by residual paramagnetic nitrogen which was determined to have a concentration of 49(7) ppm. Under ideal conditions, the shot-noise limited sensitivity is projected to be ∼ 150 fT/ √ Hz for a 100 µm-scale magnetometer based on this sample. Other samples with NV concentrations from .007 to 12 ppm and eective relaxation times ranging from 27 to over 291 ns were prepared and characterized.
We present an experimental study of the longitudinal electron-spin relaxation time (T1) of negatively charged nitrogen-vacancy (NV) ensembles in diamond. T1 was studied as a function of temperature from 5 to 475 K and magnetic field from 0 to 630 G for several samples with various NV and nitrogen concentrations. Our studies reveal three processes responsible for T1 relaxation. Above room temperature, a two-phonon Raman process dominates; below room temperature, we observe an Orbach-type process with an activation energy of 73(4) meV, which closely matches the local vibrational modes of the NV center. At yet lower temperatures, sample dependent cross-relaxation processes dominate, resulting in temperature independent values of T1 from milliseconds to minutes. The value of T1 in this limit depends sensitively on the magnetic field and can be tuned by more than 1 order of magnitude.
Radical intermediates generated in radiolysis and photoionization of ionic liquids (ILs) composed of ammonium, phosphonium, pyrrolidinium, and imidazolium cations and bis(triflyl)amide, dicyanamide, and bis(oxalato)borate anions have been studied using magnetic resonance spectroscopy. Large yields of terminal and penultimate C-centered radicals are observed in the aliphatic chains of the phosphonium, ammonium, and pyrrolidinium cations, but not for imidazolium cation. This pattern is indicative of efficient deprotonation of a hole trapped on the parent cation (the radical dication) that competes with rapid electron transfer from a nearby anion. This charge transfer leads to the formation of stable N- or O-centered radicals; the dissociation of parent anions is a minor pathway. Addition of 10-40 wt % of trialkyl phosphate (a common extraction agent) has relatively little effect on the fragmentation of the ILs. The yield of the alkyl radical fragment generated by dissociative electron attachment to the trialkyl phosphate is <4% of the yield of the radical fragments derived from the IL solvent. The import of these observations for radiation stability of the prospective nuclear cycle extraction systems based upon the ILs is discussed.
Room temperature ionic liquids (IL) find increasing use for the replacement of organic solvents in practical applications, including their use in solar cells and electrolytes for metal deposition, and as extraction solvents for the reprocessing of spent nuclear fuel. The radiation stability of ILs is an important concern for some of these applications, as previous studies suggested extensive fragmentation of the constituent ions upon irradiation. In the present study, electron paramagnetic resonance (EPR) spectroscopy has been used to identify fragmentation pathways for constituent anions in ammonium, phosphonium, and imidazolium ILs. Many of these detrimental reactions are initiated by radiation-induced redox processes involving these anions. Scission of the oxidized anions is the main fragmentation pathway for the majority of the practically important anions; (internal) proton transfer involving the aliphatic arms of these anions is a competing reaction. For perfluorinated anions, fluoride loss following dissociative electron attachment to the anion can be even more prominent than this oxidative fragmentation. Bond scission in the anion was also observed for NO(3)(-) and B(CN)(4)(-) anions and indirectly implicated for BF(4)(-) and PF(6)(-) anions. Among small anions, CF(3)SO(3)(-) and N(CN)(2)(-) are the most stable. Among larger anions, the derivatives of benzoate and imide anions were found to be relatively stable. This stability is due to suppression of the oxidative fragmentation. For benzoates, this is a consequence of the extensive sharing of unpaired electron density by the π-system in the corresponding neutral radical; for the imides, this stability could be the consequence of N-N σ(2)σ(*1) bond formation involving the parent anion. While fragmentation does not occur for these "exceptional" anions, H atom addition and electron attachment are prominent. Among the typically used constituent anions, aliphatic carboxylates were found to be the least resistant to oxidative fragmentation, followed by (di)alkyl phosphates and alkanesulfonates. The discussion of the radiation stability of ILs is continued in the second part of this study, which examines the fate of organic cations in such liquids.
In part 1 of this study, radiolytic degradation of constituent anions in ionic liquids (ILs) was examined. The present study continues the themes addressed in part 1 and examines the radiation chemistry of 1,3-dialkyl substituted imidazolium cations, which currently comprise the most practically important and versatile class of ionic liquid cations. For comparison, we also examined 1,3-dimethoxy- and 2-methyl-substituted imidazolium and 1-butyl-4-methylpyridinium cations. In addition to identification of radicals using electron paramagnetic resonance spectroscopy (EPR) and selective deuterium substitution, we analyzed stable radiolytic products using (1)H and (13)C nuclear magnetic resonance (NMR) and tandem electrospray ionization mass spectrometry (ESMS). Our EPR studies reveal rich chemistry initiated through "ionization of the ions": oxidation and the formation of radical dications in the aliphatic arms of the parent cations (leading to deprotonation and the formation of alkyl radicals in these arms) and reduction of the parent cation, yielding 2-imidazolyl radicals. The subsequent reactions of these radicals depend on the nature of the IL. If the cation is 2-substituted, the resulting 2-imidazolyl radical is relatively stable. If there is no substitution at C(2), the radical then either is protonated or reacts with the parent cation forming a C(2)-C(2) σσ*-bound dimer radical cation. In addition to these reactions, when methoxy or C(α)-substituted alkyl groups occupy the N(1,3) positions, their elimination is observed. The elimination of methyl groups from N(1,3) was not observed. Product analyses of imidazolium liquids irradiated in the very-high-dose regime (6.7 MGy) reveal several detrimental processes, including volatilization, acidification, and oligomerization. The latter yields a polymer with m/z of 650 ± 300 whose radiolytic yield increases with dose (~0.23 monomer units per 100 eV for 1-methyl-3-butylimidazolium trifluorosulfonate). Gradual generation of this polymer accounts for the steady increase in the viscosity of the ILs upon irradiation. Previous studies at lower dose have missed this species due to its wide mass distribution (stretching out to m/z 1600) and broad NMR lines, which make it harder to detect at lower concentrations. Among other observed changes is the formation of water immiscible fractions in hydrophilic ILs and water miscible fractions in hydrophobic ILs. The latter is due to anion fragmentation. The import of these observations for use of ILs as extraction solvents in nuclear cycle separations is discussed.
A photocatalytic hydrogen-evolving system based on intermolecular electron transfer between native Photosystem I (PSI) and electrostatically associated Pt nanoparticles is reported. Using cytochrome c6 as the soluble mediator and ascorbate as the sacrificial electron donor, visible-light-induced H2 production occurs for PSI/Pt nanoparticle biohybrids at a rate of 244 μmol H2 (mg chlorophyll)−1 h−1 or 21 034 mol H2 (mole PSI)−1 h−1. These results demonstrate that highly efficient photocatalysis of H2 can be obtained for a self-assembled, noncovalent complex between PSI and Pt nanoparticles; a molecular wire between the terminal acceptor of PSI, the [4Fe−4S] cluster FB, and the nanoparticle is not required. EPR characterization of the electron-transfer reactions in PSI/Pt nanoparticle biohybrids shows blocked electron transfer to flavodoxin, the native acceptor protein of PSI, and presents evidence of low-temperature photogenerated electron transfer between PSI and the Pt nanoparticle. This work demonstrates a feasible strategy for linking molecular catalysts to PSI that takes advantage of electrostatic-directed assembly to mimic acceptor protein binding.
Light induced reactions of carboxylic, hydroxycarboxylic, and aminocarboxylic acids, carboxylated aromatics, and α-amino acids and peptides adsorbed on hydrated anatase (TiO2), goethite (α-FeOOH), and hematite (α-Fe2O3) have been studied at low temperature (77−200 K), by means of electron paramagnetic resonance (EPR) spectroscopy, and at 295 K, by means of transient absorption spectroscopy. In the room-temperature solution, the photocatalytic decomposition of carboxylated molecules, in the absence of synergistic adsorption by hydroxyl groups (e.g., in serine), is inefficient due to weak surface binding. The yield of radical formation increases significantly at low temperature, as the carboxylated molecules adsorb on the surface. The main photodegradation path is decarboxylation initiated by charge transfer from the metal oxide to the adsorbate. Below 120 K, for carboxylic acids and nonaromatic amino acids and peptides, the decarboxylation is the only reaction pathway, yielding the corresponding C-centered radicals. At higher temperature these radicals become mobile and abstract H from the parent molecules. For aromatic amino acids (histidine, tyrosine, and tryptophan) charge transfer followed by deprotonation is the predominant photoreaction. For polycarboxylated aromatics, the outcome of the charge transfer is determined by the stability of the trapped-hole species. In addition to trapping holes, some adsorbates, such as mellitic acid, trap surface electrons. The photocatalytic activity of the anatase, goethite, and hematite are similar for aromatic, carboxylic, and hydroxycarboxylic acids; for hematite, this activity reduces markedly for α-amino acids and peptides. The rutile is inactive toward these carboxylated molecules. These findings are related to martian soil chemistry, biomedical chemistry, and photocatalysis.
We propose that the paucity of organic compounds in martian soil can be accounted for by efficient photocatalytic decomposition of carboxylated molecules due to the occurrence of the photo-Kolbe reaction at the surface of particulate iron(III) oxides that are abundant in the martian regolith. This photoreaction is initiated by the absorption of UVA light, and it readily occurs even at low temperature. The decarboxylation is observed for miscellaneous organic carboxylates, including the nonvolatile products of kerogen oxidation (that are currently thought to accumulate in the soil) as well as alpha-amino acids and peptides. Our study indicates that there may be no "safe haven" for these organic compounds on Mars; oxidation by reactive radicals, such as hydroxyl, is concerted with photocatalytic reactions on the oxide particles. Acting together, these two mechanisms result in mineralization of the organic component. The photooxidation of acetate (the terminal product of radical oxidation of the aliphatic component of kerogen) on the iron(III) oxides results in the formation of methane; this reaction may account for seasonably variable production of methane on Mars. The concomitant reduction of Fe(III) in the regolith leads to the formation of highly soluble ferrous ions that contribute to weathering of the soil particles.
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