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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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The reactions of ortho-benzyne ( o -C 6 H 4 ) with resonance-stabilized radicals lead to multiring species and specifically 5-member-rings, contributing to molecular-weight growth and production of curved PAHs.
Correction for ‘Impact of lanthanide ion complexation and temperature on the chemical reactivity of N , N , N ′, N ′-tetraoctyl diglycolamide (TODGA) with the dodecane radical cation’ by Gregory P. Horne et al. , Phys. Chem. Chem. Phys. , 2023, 25 , 16404–16413, https://doi.org/10.1039/D3CP01119D.
Heterogeneous photocatalysts (PCs) have garnered attention for their sustainability and cost-effectiveness. Despite the existence of various types of these PCs, their synthesis often involves complex, multi-step procedures and laborious purification. Herein, we propose a simple method for attaching small-molecule photocatalytic species onto crosslinked 3-D polymer networks as insoluble scaffolds to create robust heterogeneous PCs. The highly swellable poly(ethylene glycol)-based ChemMatrix (CM) resin, known for its amphiphilic properties and high functional group loading, facilitated the covalent immobilization of the photoredox dye Eosin Y (EY), but also streamlined functionalization with Ir( III ) complexes. The resulting heterogeneous CM-EY demonstrated efficient photocatalytic performance in open-to-air dual photoredox catalysis of atom transfer radical polymerization (photo-ATRP) under green light. This was confirmed by the well-controlled synthesis of polymers with molecular masses ranging from 20 kDa to 300 kDa and low dispersities. Furthermore, CM-EY exhibited excellent photostability and recyclability over multiple cycles of ATRP. The heterogeneous catalysis of photo-ATRP provided high temporal control and enabled benign conditions for synthesizing protein-polymer hybrids (PPH). When combined with the initiator-modified CM (CM-BIB), CM-EY facilitated the solid-phase synthesis of homopolymers and block copolymers with recyclable performance. However, the coordinatively bound Ir@CM showed decreased catalytic activity and efficiency toward photoredox dehalogenation due to the leaching of active species during recycling. This study highlights the advantages of the covalent linking of catalysts to solid supports over non-covalent interactions, underscoring the potential of functionalized polymer resin as a promising scaffold. Such an approach offers customization and tunability, presenting opportunities for innovation in green chemistry.
The stepwise reduction by 1–3 electrons of a π-expanded pyracylene with K and Rb reveals that in-build core asymmetry affects the spin-density distribution in the mono- and trianion radicals, as confirmed by EPR spectroscopy and DFT calculations.
Nitroxide-radicals such as 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) and their derivatives have gained interest as redox-active organic molecules for applications in grid-scale energy storage. In particular, the higher solubility of 4-hydroxy-TEMPO in aqueous media greatly improves its energy density, but unusual kinetics associated with its surface-mediated electrooxidation have limited further development. Here, the apparent passivation behavior of species formed during 4-hydroxy-TEMPO electrooxidation in concentrated electrolytes is investigated. A combination of surface microscopy, X-ray photoelectron spectroscopy, and quartz-crystal gravimetry confirms the formation of a polymeric-type layer over the electrode surface composed of 4-hydroxy-TEMPO-like subunits, which is otherwise not observed with TEMPO. This study indicates that the design of high energy density and stable TEMPO-based redox molecules must also consider the reactivity that may occur due to the molecular characteristics of solubility-enhancing moieties. It is found that the extent of passivation is dependent on the voltage scan rate and 4-hydroxy-TEMPO concentration, underscoring the importance of studying materials at conditions relevant for their proposed applications. Evidence of incomplete passivation and an electrode self-cleaning process is presented, suggesting a materials design strategy to mitigate surface passivation from side reactions that may occur in redox active materials for energy storage applications.
State-specific orbital optimized approaches are more accurate at predicting core-level spectra than traditional linear-response protocols, but their utility had been restricted due to the risk of "variational collapse" down to the ground state. We employ the recently developed square gradient minimization algorithm to reliably avoid variational collapse and study the effectiveness of orbital optimized density functional theory (DFT) at predicting second period element 1s core-level spectra of open-shell systems. Several density functionals (including SCAN, B3LYP, and ωB97X-D3) are found to predict excitation energies from the core to singly occupied levels with high accuracy (≤0.3 eV RMS error) against available experimental data. Higher excited states are, however, more challenging by virtue of being intrinsically multiconfigurational. We thus present a configuration interaction inspired route to self-consistently recouple single determinant mixed configurations obtained from DFT, in order to obtain approximate doublet states. This recoupling scheme is used to predict the C K-edge spectra of the allyl radical, the O K-edge spectra of CO + , and the N K-edge of NO 2 with high accuracy relative to experiment, indicating substantial promise in using this approach for the computation of core-level spectra for doublet species [vs more traditional time dependent DFT, equation of motion coupled cluster singles and doubles (EOM-CCSD), or using unrecoupled mixed configurations]. Finally, we also present general guidelines for computing core-excited states from orbital optimized DFT.
Photogenerated spin-correlated radical pairs (SCRPs) in electron donor–bridge–acceptor (D–B–A) molecules can act as molecular qubits and inherently spin qubit pairs. SCRPs can take singlet and triplet spin states, comprising the quantum superposition state. Their synthetic accessibility and well-defined structures, together with their ability to be prepared in an initially pure, entangled spin state and optical addressability, make them one of the promising avenues for advancing quantum information science. Coherence between two spin states and spin selective electron transfer reactions form the foundation of using SCRPs as qubits for sensing. We can exploit the unique sensitivity of the spin dynamics of SCRPs to external magnetic fields for sensing applications including resolution-enhanced imaging, magnetometers, and magnetic switch. Molecular quantum sensors, if realized, can provide new technological developments beyond what is possible with classical counterparts. While the community of spin chemistry has actively investigated magnetic field effects on chemical reactions via SCRPs for several decades, we have not yet fully exploited the synthetic tunability of molecular systems to our advantage. This review offers an introduction to the photogenerated SCRPs-based molecular qubits for quantum sensing, aiming to lay the foundation for researchers new to the field and provide a basic reference for researchers active in the field. We focus on the basic principles necessary to construct molecular qubits based on SCRPs and the examples in quantum sensing explored to date from the perspective of the experimentalist.
Polariton chemistry may provide a new means to control molecular reactivity, permitting remote, reversible modification of reaction energetics, kinetics, and product yields. A considerable body of experimental and theoretical work has already demonstrated that strong coupling between a molecular vibrational mode and the confined electromagnetic field of an optical cavity can alter chemical reactivity without external illumination. However, the mechanisms underlying cavity-altered chemistry remain unclear in large part because the experimental systems examined previously are too complex for detailed analysis of their reaction dynamics. Here, we experimentally investigate photolysis-induced reactions of cyanide radicals with strongly-coupled chloroform (CHCl 3 ) solvent molecules and examine the intracavity rates of photofragment recombination, solvent complexation, and hydrogen abstraction. Here we use a microfluidic optical cavity fitted with dichroic mirrors to facilitate vibrational strong coupling (VSC) of the C–H stretching mode of CHCl 3 while simultaneously permitting optical access at visible wavelengths. Ultrafast transient absorption experiments performed with cavities tuned on- and off-resonance reveal that VSC of the CHCl 3 C–H stretching transition does not significantly modify any measured rate constants, including those associated with the hydrogen abstraction reaction. This work represents, to the best of our knowledge, the first experimental study of an elementary bimolecular reaction under VSC. We discuss how the conspicuous absence of cavity-altered effects in this system may provide insights into the mechanisms of modified ground state reactivity under VSC and help bridge the divide between experimental results and theoretical predictions in vibrational polariton chemistry.
Here, we investigate the dynamics and site-selectivity in the dissociation of transient anions formed upon attachment of low energy electrons to acetic acid by anion fragment momentum imaging experiments. The resonances at 6.7 and 7.7 eV are confirmed to dissociate exclusively by the O–H bond, while a third resonance at 9.1 eV dissociates primarily by both C–H break and O–H break. A fourth resonance near 10 eV is found to dissociate by O–H break. For each resonance, the measured kinetic energy release indicates two-body dissociation produces a neutral radical in the ground electronic state, for all four resonances. The measured angular distributions are consistent with all four resonances having A' symmetry.
Photosystem II (PSII) is an intrinsic membrane protein complex that functions as a light-driven water:plastoquinone oxidoreductase in oxygenic photosynthesis. Electron transport in PSII is associated with formation of reactive oxygen species (ROS) responsible for oxidative modifications of PSII proteins. In this study, oxidative modifications of the D1 and D2 proteins by the superoxide anion (O 2 •- ) and the hydroxyl (HO•) radicals were studied in WT and a tocopherol cyclase (vte1) mutant, which is deficient in the lipid-soluble antioxidant α-tocopherol. In the absence of this antioxidant, high-resolution tandem mass spectrometry was used to identify oxidation of D1: 130 E to hydroxyglutamic acid by O 2 •- at the Pheo D1 site. Additionally, D1: 246 Y was modified to either tyrosine hydroperoxide or dihydroxyphenylalanine by O 2 •- and HO • , respectively, in the vicinity of the nonheme iron. We propose that α-tocopherol is localized near PheoD1 and the nonheme iron, with its chromanol head exposed to the lipid–water interface. This helps to prevent oxidative modification of the amino acid’s hydrogen that is bonded to PheoD1 and the nonheme iron (via bicarbonate), and thus protects electron transport in PSII from ROS damage.
Formate has great potential to function as a feedstock for biorefineries because it can be sustainably produced by a variety of processes that don’t compete with agricultural production. However, naturally formatotrophic organisms are unsuitable for large-scale cultivation, difficult to engineer, or have inefficient native formate assimilation pathways. Thus, metabolic engineering needs to be developed for model industrial organisms to enable efficient formatotrophic growth. Here, we build a prototype synthetic formate utilizing bacterial microcompartment (sFUT) encapsulating the oxygen-sensitive glycyl radical enzyme pyruvate formate lyase and a phosphate acyltransferase to convert formate and acetyl-phosphate into the central biosynthetic intermediate pyruvate. This metabolic module offers a defined environment with a private cofactor coenzyme A that can cycle efficiently between the encapsulated enzymes. To facilitate initial design-build-test-refine cycles to construct an active metabolic core, we used a “wiffleball” architecture, defined as an icosahedral bacterial microcompartment (BMC) shell with unoccupied pentameric vertices to freely permit substrate and product exchange. The resulting sFUT prototype wiffleball is an active multi enzyme synthetic BMC functioning as platform technology.
Polycyclic Aromatic Hydrocarbons (PAHs) have been invoked in fundamental molecular mass growth processes in our galaxy. We provide compelling evidence of the formation of the very first ringed aromatic and building block of PAHs - benzene - via the self-recombination of two resonantly stabilized propargyl (C 3 H 3 ) radicals in dilute environments using isomer selective synchrotron-based mass spectrometry coupled to theoretical calculations. Along with benzene, three other structural isomers (1,5-hexadiyne, fulvene, 2-ethynyl-1,3-butadiene) and o-benzyne are detected and their branching ratios quantified experimentally and verified with the aid of computational fluid dynamics and kinetic simulations. Furthermore, these results uncover molecular growth pathways not only in interstellar, circumstellar, and solar systems environments, but also in combustion systems gaining us a better understanding of the hydrocarbon chemistry of our universe.
Organic aerosol (OA) is an air pollutant ubiquitous in urban atmospheres. Urban OA is usually apportioned into primary OA (POA), mostly emitted by mobile sources, and secondary OA (SOA), which forms in the atmosphere due to oxidation of gas-phase precursors from anthropogenic and biogenic sources. By performing coordinated measurements in the particle phase and the gas phase, we show that the alkylperoxy radical chemistry that is responsible for low-temperature ignition also leads to the formation of oxygenated POA (OxyPOA). OxyPOA is distinct from POA emitted during high-temperature ignition and is chemically similar to SOA. We present evidence for the prevalence of OxyPOA in emissions of a spark-ignition engine and a next-generation advanced compression-ignition engine, highlighting the importance of understanding OxyPOA for predicting urban air pollution patterns in current and future atmospheres.
ABSTRACT Methyl-coenzyme M reductase (MCR), the key catalyst in the anoxic production and consumption of methane, contains an unusual 2-methylglutamine residue within its active site. In vitro data show that a B12-dependent radical SAM (rSAM) enzyme, designated MgmA, is responsible for this post-translational modification (PTM). Here, we show that two different MgmA homologs are able to methylate MCR in vivo when expressed in Methanosarcina acetivorans , an organism that does not normally possess this PTM. M. acetivorans strains expressing MgmA showed small, but significant, reductions in growth rates and yields on methylotrophic substrates. Structural characterization of the Ni(II) form of Gln-methylated M. acetivorans MCR revealed no significant differences in the protein fold between the modified and unmodified enzyme; however, the purified enzyme contained the heterodisulfide reaction product, as opposed to the free cofactors found in eight prior M. acetivorans MCR structures, suggesting that substrate/product binding is altered in the modified enzyme. Structural characterization of MgmA revealed a fold similar to other B12-dependent rSAMs, with a wide active site cleft capable of binding an McrA peptide in an extended, linear conformation. IMPORTANCE Methane plays a key role in the global carbon cycle and is an important driver of climate change. Because MCR is responsible for nearly all biological methane production and most anoxic methane consumption, it plays a major role in setting the atmospheric levels of this important greenhouse gas. Thus, a detailed understanding of this enzyme is critical for the development of methane mitigation strategies.
Deep eutectic solvents (DESs) are emerging as promising electrolytes for electrochemical energy storage applications. Electroactive nitroxide-radical-containing organics can be dissolved in DESs to facilitate redox reactions; however, mechanistic know-how of their charge transfer kinetics at the electrode surface is rather limited. Here, we investigate the mechanism underlying the electrochemical oxidation of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl (4-hydroxy-TEMPO). Using polarization measurements on a platinum rotating disk electrode and micro-electrode, we show that the anodic charge transfer coefficient (a) for one-electron transfer oxidations of TEMPO and4-hydroxy-TEMPO approaches 0.9 in DES as well as in aqueous electrolytes, i.e., a significant deviation fromα≈0.5 expected for symmetric redox behavior. To explain this observation, a two-step oxidation mechanism is proposed wherein the nitroxide-containing species undergo fast charge transfer at an electrode surface followed by slow rate-limiting desorption of the adsorbed oxidized species. Numerical simulations are reported to characterize how the proposed two-step mechanism manifests intransient cyclic voltammetry behavior of the 4-hydroxy-TEMPO oxidation reaction, and good agreement with experiments is noted.
Electroactive coatings based on non-conjugated redox-active polymers have increased in popularity with the development of thin film organic batteries. Here, control over coating deposition, redox-activity, and ion transport are key to improving their energy storage performance. In this work, the synthesis, solution state electrochemical characterization, and layer-by-layer (LbL) assembly of a nitroxide-based polycation and polyanion are presented. Solution state electrochemical characterization indicates that the rate of electron transfer for the nitroxide polyanion is much higher as compared to the nitroxide polycation. LbL thin films of the nitroxide polyanion and nitroxide polycation are assembled, demonstrating linear growth and tunable thickness (28 nm/layer pair). This work confirms that the ion transport mechanism of the LbL films during the redox reaction is influenced depending on the charge of the terminating layer, where the nitroxide polyanion can participate in self-doping, which leads to a contribution from cation transport. The nitroxide polyanion-terminated film also exhibits a higher capacity and a slightly reduced charge transfer resistance. However, it was also observed that a more pronounced capacity fade occurred for the polyanion-terminated film than the polycation-terminated film. Taken together, this highlights how oppositely charged radical-containing polyelectrolytes can form electroactive coatings for possible applications in energy storage or sensing.
Organic compounds containing nitroxide radicals such as 4–hydroxy–2,2,6,6–tetramethylpiperidine–1–oxyl (4–hydroxy–TEMPO) are redox–active and are of interest for potential applications in redox flow batteries. The mechanisms governing charge–transfer reactions of such compounds are not well understood. Specifically, the anodic charge transfer coefficient (αa) corresponding to the electro–oxidation of 4–hydroxy–TEMPO in an aqueous medium is ~0.9, i.e., αa deviates considerably from the expected value (0.5) for a symmetric single–step one–electron transfer redox reaction. In a previous publication (J. Electrochem. Soc., 2020, 167, 143505), we have proposed a reaction mechanism to explain such asymmetric behavior by invoking adsorption–desorption processes. In the proposed mechanism, reversible oxidation of 4–hydroxy–TEMPO leads to the adsorption of the oxidation product, which then undergoes slow rate–limiting desorption from the electrode surface. In the present contribution, supporting evidence is provided for this mechanism. In situ surface–enhanced Raman spectroscopy combined with density functional theory simulations are employed to confirm the presence of surface–adsorbed species at a Au electrode during electro–oxidation of 4–hydroxy–TEMPO. Furthermore, we employ chronopotentiometry to track the gradual re–equilibration of the electrode–electrolyte interface following the electro–oxidation of 4–hydroxy–TEMPO. Analysis of the chronopotentiometry data further suggests the presence of adsorbed species, which were previously proposed and are now confirmed by direct spectroscopic evidence.
In this work we studied OH radical generation in nanosecond dielectric barrier discharge in humid He/air gas. The measurements were carried out by means of laser-induced fluorescence (LIF) method at the PPPL Low Temperature Plasma Research Facility, directed by Dr. Shurik Yatom. Application of LIF towards OH density measurements is a widely used approach in plasmas generated in humid gas, particularly when temporal evolution of OH density is of interest. Here we examined the OH densities generated in the discharge ignited by application of nanosecond high-voltage pulses with amplitudes varying between 10 to 20 kV and interelectrode gap length varying between 0.5-3 mm. The peak voltage and the gap length determine the mode in which discharge is generated: homogenous or filamentary. The measurements of OH in the gas phase were accompanied by the measurements of hydrogen peroxide (H 2 O 2 ) in liquid water, downstream of the plasma and the relationship between these two were examined.