Biomass RNA for the Controlled Synthesis of Degradable Networks by Radical Polymerization
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
SEARCH · Search NASA
Results for “Free radicals”
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.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Effect of frequency and applied voltage of an atmospheric-pressure dielectric-barrier discharge on breakdown and hydroxyl-radical generation with a liquid electrode
This work examines the effect of the frequency and peak applied voltage on hydroxyl-radical generation in a dielectric-barrier plasma discharge between a metallic needle electrode and one electrode covered with dielectric. The authors examine a system that can expose up to 96 liquid samples in an automated fashion without human intervention beyond setting the initial software configuration. Then, hydroxylradical concentration, measured through coumarin fluorescence, was measured for 5 s plasma exposures generated under different highvoltage conditions with frequencies from 2 to 16 kHz and amplitudes from 4 to 9 kV. Their results show that an increase in frequency and/or applied voltage, within the range prescribed above and the limits of the high-voltage power supply, can yield up to a 150% increase in fluorescence with an equivalent hydroxyl-radical increase. Applications using typical previous methods, such as the Fenton Reaction, are limited in that they continuously generate hydroxyl radicals over millisecond and longer intervals. These results establish the electrical parameters that can now be applied to polymers, like proteins, which show three dimensional structures that are flexible and fluctuate on a microsecond and nanosecond time scale, with hydroxyl-radical generation on this time scale using this device. Additionally, plasma exposures may be optimized for a great variety of proteins, devices and techniques, where hydroxyl-radical generation is of utmost importance, reducing exposure time and potential subjection of samples to harmful side effects.
42 ENGINEERING↗
Multiscale modelling of the radical-induced chemistry of acetohydroxamic acid in aqueous solution
A comprehensive multiscale model determines the fundamental reaction mechanisms of the radical-induced degradation of acetohydroxamic acid in acidic aqueous solutions.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Energetics and mechanisms for the acetonyl radical + O 2 reaction: An important system for atmospheric and combustion chemistry
The acetonyl radical (•CH 2 COCH 3 ) is relevant to atmospheric and combustion chemistry due to its prevalence in many important reaction mechanisms. One such reaction mechanism is the decomposition of Criegee intermediates in the atmosphere that can produce acetonyl radical and OH. In order to understand the fate of the acetonyl radical in these environments and to create more accurate kinetics models, we have examined the reaction system of the acetonyl radical with O 2 using highly reliable theoretical methods. Structures were optimized using coupled cluster theory with singles, doubles, and perturbative triples [CCSD(T)] with an atomic natural orbital (ANO0) basis set. Energetics were computed to chemical accuracy using the focal point approach involving perturbative treatment of quadruple excitations [CCSDT(Q)] and basis sets as large as cc-pV5Z. The addition of O 2 to the acetonyl radical produces the acetonylperoxy radical, and multireference computations on this reaction suggest it to be barrierless. Additionally, no submerged pathways were found for the unimolecular isomerization of the acetonylperoxy radical. Besides dissociation to reactants, the lowest energy pathway available for the acetonylperoxy radical is a 1-5 H shift from the methyl group to the peroxy group through a transition state that is 3.3 kcal mol -1 higher in energy than acetonyl radical + O 2 . The ultimate products from this pathway are the enol tautomer of the acetonyl radical along with O 2 . Multiple pathways that lead to OH formation are considered; however, all of these pathways are predicted to be energetically inaccessible, except at high temperatures.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
On electron beam-induced degradation of vinyl ester thermosets
We have demonstrated that electron beam radiolysis induces scissions of the C-O-C bonds along the backbone of the chains of unsaturated polyester thermosets of different compositions based on dicyclopentadiene, isophthalic acid, epoxy vinyl ester, and terephthalic acid. The radiolysis is imminent irrespective of the degree of crosslinking in the thermosets both in neat resins and in the presence of solvents. Electron Paramagnetic Resonance (EPR) results show the formation of the alkoxyl radicals and C-centered radicals as the primary intermediate products of the C-O-C scissions. While the alkoxyl radicals of these resins exhibit very good stability even six months after the irradiation, the C-centered radicals decay very rapidly via their reactions with oxygen that is available either as adsorbed in the resins, dissolved in solvents or from the environment. The radiolytically produced •OH radicals in the unsaturated-ester aqueous solutions play a major role in inducing scissions on the backbone of the polymer chains. The solvated electrons (e s ) from organic solvents, such as dimethyl sulfoxide and isopropyl alcohol, also induce direct scission of the C-O-C bonds, giving rise to the formation of alkoxyl radicals and C-centered radicals. However, a considerable fraction of es is scavenged by the dissolved O 2 to produce O 2 - . Despite the radiation-induced scissions, irradiation of the resins at a dose level of 1000 kGy results in an increase of the glass transition temperature, Tg. This is due to the simultaneous radiation-induced polymerization of the vinyl monomers, toluene, and styrene that are present in the resins. The increase in Tg is observed in all the resins except for the terephthalic polyester resin in aqueous solution, in which the absence of these monomers results in Tg decreasing sharply with irradiation. This work demonstrates that ionizing radiation triggers continuous free radical-chain reactions that lead to the formation of recyclable oligomers.
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
The role of collisional energy transfer in the thermal and prompt dissociation of 1-methyl allyl
Collisional energy transfer plays a pivotal role in a-priori calculations of the pressure-dependent rate constants obtained from a master equation. However, accurate determinations of collisional energy transfer parameters are rare and so most kinetic studies rely on best-fits of these parameters to experimental measurements (if available) or estimates guided from literature studies. In this work, we have quantified the effect of the uncertainty in energy transfer parameters on the thermal and prompt dissociation kinetics of a resonance stabilized radical, 1-methyl allyl (1MA), of relevance to the combustion of 1- and 2-butene isomers. Simulations using literature kinetics models were performed to assess the impact of these uncertainties on flame propagation and speciation data in laminar flames of 1- and 2-butene. Analyses of the uncertainty propagated by the energy transfer parameters for 1MA dissociation to the flame simulations, in particular the laminar flame speed, indicate an intricate coupling between the kinetics of 1MA dissociation (chain propagation) and its reaction with H-atoms (chain-termination). Ab-initio based theoretical calculations were also performed to obtain pressure-dependent kinetics for the reaction of 1MA with H-atoms. Lastly, theoretically calculated energy transfer parameters were used to best characterize the kinetics and branching between the chain propagating 1MA dissociation and the chain-terminating reaction 1MA + H.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Automated identification and calculation of prompt effects in kinetic mechanisms using statistical models
The kinetics of prompt dissociation involves rovibrationally excited species (generally formed by exothermic reactions) which may dissociate or isomerize prior to thermalization via collisions with the bath gas. Treating such rovibrationally excited species (so-called "hot" species) with standard kinetic phenomenology may result in incorrect macroscopic representation of their reactivity. Here this work presents the first fully automated methodology for the calculation of prompt effects of a chosen species in a kinetic mechanism, including (i) reaction selection; (ii) theoretical calculation of rate constants and prompt branching fractions; and (iii) final rate constant fitting. The energy partition between hot fragments is estimated using a variety of statistical models, including a new physically sound microcanonical statistical model based on the rovibrational density of states of the fragments. The methodology is validated against literature data for the prompt dissociations of HCO and C 3 H 7 radicals. The microcanonical statistical model is in better agreement with trajectory simulations for larger species and is thus applicable for practical systems that typically involve large molecules, for which direct dynamics calculations are impractical. The automated workflow is applied to the evaluation of the effects of prompt dissociation for two isomeric radicals C 4 H 7 1-3 (1-methylallyl) and C 4 H 7 1-4 (3-buten-1-yl). Twelve H-atom abstraction reactions are selected and the corresponding rate constants are computed with first principles theory. The microcanonical statistical model predicts that prompt dissociations of C 4 H 7 1-3 and C 4 H 7 1-4 are already significant at 1000K, resulting in differences of up to an order of magnitude at 2000K with respect to the phenomenological thermal rate constants. To illustrate the effects of prompt dissociation on simulations of experimental data, the calculated prompt rate constants are implemented in both CRECK and C3MechV3.3 kinetic mechanisms. Simulations of experimental flame data illustrate the noticeable impact of prompt dissociation kinetics on the high-temperature combustion reactivity of C 4 H 8 -1 and C 4 H 8 -2.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Breaking C-C Bonds via Electrochemically Mediated Hydrogen Atom Transfer Reactions
Cleaving inert SP3-SP3 carbon-carbon (C-C) bonds selectively remains a major challenge in organic chemistry and a main bottleneck in the chemical upcycling of recalcitrant polyolefin waste. Here, we present an electrochemical strategy using redox mediators to activate and break C-C bonds at room temperature and ambient pressure. Specifically, we use N-hydroxyphthalimide (NHPI) as a redox mediator that undergoes electrochemical oxidation to form the phthalimide-N-oxyl (PINO) radical to initiate hydrogen atom transfer (HAT) reactions with benzylic C-H bonds. The resulting benzylic carbon radical is readily captured by molecular oxygen to form a peroxy radical that decomposes into oxygenated C-C bond-scission fragments. This indirect, mediated approach for Csp3-Csp3 bond cleavage reduces the oxidation potential by > 1.2 V compared to the direct oxidation of the substrate, thereby eliminating deleterious side reactions, such as solvent oxidation, that may occur at high potentials. Studies with a bibenzyl model compound revealed a bifurcated reaction pathway following the initial HAT step. At a bibenzyl conversion of 61.0%, the C-C bond cleavage pathway generates benzaldehyde and benzoic acid products at 38.4% selectivity, and the C-H bond oxygenation pathway leads to 1,2-diphenylethanone and benzil products at 39.2% selectivity. Changes in reaction selectivity were investigated with various model compounds, including bibenzyl, 1,3-diphe-nylpropane, 1,4-diphenylbutane, and their derivatives. Product selectivity is correlated with the C-C bond strength of the reactant, with weaker C-C bonds favoring the C-C bond cleavage pathway. We also evaluated the mediated oxidation of oligo-meric styrene (Mn= 510 Da, OS510) which were converted into oxygenated products. Lastly, proof-of-concept depolymeriza-tion of polystyrene (PS, ~10,000 Da) into oxygenated monomers, dimers, and oligomers was demonstrated using NHPI-mediated oxidation.
benzoic acid↗
Experimental and theoretical studies of the doubly substituted methyl-ethyl Criegee intermediate: Infrared action spectroscopy and unimolecular decay to OH radical products
In this work the infrared (IR) action spectrum of the doubly substituted methyl-ethyl Criegee intermediate (MECI) is observed in the CH stretch overtone region with detection of OH products. The MECI exhibits four conformers, all of which undergo unimolecular decay via a 1,4 H-atom transfer mechanism, followed by the rapid release of OH products. Conformers with different orientations of the carbonyl oxide group with respect to the methyl and ethyl substituents (i.e., anti and syn ) decay via distinct transition state barriers (16.1 kcal mol –1 and 15.4 kcal mol –1 , respectively). The observed IR action spectrum is in good agreement with the predicted anharmonic IR absorption spectrum, but exhibits significant congestion, which is attributed to couplings between spectroscopic bright states and nearby dark states. Energy-dependent OH appearance rates are measured upon IR excitation of the strongest features in the IR action spectrum and are found to be on the order of 10 6 –10 7 s –1 . The experimental rates are in good agreement with computed Rice–Ramsperger–Kassel–Marcus rates for the unimolecular decay of MECI at these energies, which incorporate quantum mechanical tunneling and sophisticated hindered rotor treatments, as well as high-level theoretical calculations of the TS barrier heights, rovibrational properties, and torsional barriers associated with the MECI conformers. Master equation modeling is used to predict thermal rates for the unimolecular decay of anti - and syn -MECI of 473 s –1 and 660 s –1 , respectively. Comparison with other previously studied Criegee intermediate systems provides insights into substituent effects on unimolecular decay under both energy-dependent and thermal conditions.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Transient hydroperoxyalkyl intermediates (•QOOH) in isopentane oxidation. I. Conformer- and isomer-resolved infrared spectra
Transient carbon-centered hydroperoxyalkyl intermediates (•QOOH) in isopentane oxidation are characterized by infrared (IR) action spectroscopy under jet-cooled conditions with selective detection of hydroxyl (OH) radical products. Two distinct •QOOH isomers with radical sites at a primary carbon of one of the methyl groups (β-Me) or a secondary carbon (β-Et) of the ethyl group are identified by comparison with theoretically calculated IR absorption features for multiple conformers, including C–O, ethyl, and O–O torsions of the two isomers. Here, a master-equation analysis is developed and utilized to explore the conformational cooling process and the resultant conformer population distributions of the two isomers. Most of the IR features observed, including those in the strong fundamental and first overtone OH stretch regions as well as weaker combination bands involving OH stretch with torsion or OOH bend, are in good accord with computed anharmonic frequencies for the most populated conformers of the •QOOH_Et isomer. Relatively weak IR features most evident in the fundamental and first overtone OH stretch regions are ascribed to multiple conformers of the less stable •QOOH_Me isomer, along with a weak feature that is uniquely attributed to a combination band involving asymmetric CH 2 stretch and HCH bend of •QOOH_Me.
Chemical reaction jet spectroscopy↗
A Stable, Low Permeable TEMPO Catholyte for Aqueous Total Organic Redox Flow Batteries
We report aqueous organic redox flow batteries (AORFBs) are highly attractive for large-scale energy storage because of their nonflammability, low cost, and sustainability. (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl (TEMPO) derivatives, a class of redox active molecules bearing air-stable free nitroxyl radicals and high redox potential (>0.8 V vs NHE), has been identified as promising catholytes for AORFBs. However, reported TEMPO based molecules are either permeable through ion exchange membranes or not chemically stable enough for long-term energy storage. Herein, a new TEMPO derivative functionalized with a dual-ammonium dicationic group, N 1 , N 1 , N 1 , N 3 , N 3 , 2, 2, 6, 6-nonamethyl-N 3 -(piperidinyloxy)propane-1,3-bis(ammonium) dichloride (N 2 -TEMPO) as a stable, low permeable catholyte for AORFBs is reported. Ultraviolet–visible (UV–vis) and proton nuclear magnetic resonance ( 1 H-NMR) spectroscopic studies reveal its exceptional stability and ultra-low permeability (1.49 × 10 -12 cm 2 s -1 ). Coupled with 1,1'-bis[3-(trimethylammonio)propyl]-4,4'-bipyridinium tetrachloride ((NPr) 2 V) as an anolyte, a 1.35 V N2-TEMPO/(NPr)2V AORFB with 0.5 m electrolytes (9.05 Wh L -1 ) delivers a high power density of 114 mW cm -2 and 100% capacity retention for 400 cycles at 60 mA cm-2. At 1.0 m electrolyte concentrations, the N 2 -TEMPO/(NPr) 2 V AORFB achieves an energy density of 18.1 Wh L -1 and capacity retention of 90% for 400 cycles at 60 mA cm -2 .
TEMPO↗
Metabolites of Tobacco- and E-Cigarette-Related Nitrosamines Can Drive Cu 2+ -Mediated DNA Oxidation
Nitrosamine metabolites resulting from cigarette smoking and E-cigarette (E-cig) vaping cause DNA damage that can lead to genotoxicity. While DNA adducts of metabolites of nitrosamines 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) and N-nitrosonornicotine (NNN) are well-known tobacco-related cancer biomarkers, only a few studies implicate NNN and NNK in DNA oxidation in humans. NNK and NNN were found in the urine of E-cigarette users who never smoked cigarettes. This paper proposes the first chemical pathways of DNA oxidation driven by NNK and NNN metabolites in redox reactions with Cu 2+ and NADPH leading to reactive oxygen species (ROS). A microfluidic array with thin films of DNA and metabolic enzymes that make metabolites of NNN and NNK in the presence of Cu 2+ and NADPH was used to estimate relative rates of DNA oxidation. Detection by electrochemiluminescence (ECL) employed a new ECL dye [Os(tpy-benz-COOH) 2 ] 2+ that is selective for and sensitive to the primary DNA oxidation product 8-oxo-7,8-dihydro-2-deoxyguanosine (8-oxodG) in DNA. Enzyme–DNA films on magnetic beads were used to produce nitrosamine metabolites that enter ROS-forming redox cycles with Cu 2+ and NADPH, and liquid chromatography–mass spectrometry (LC–MS) was used to quantify 8-oxodG and identify metabolites. ROS were detected by optical sensors. Metabolites of NNK and NNN + Cu 2+ + NADPH generated relatively high rates of DNA oxidation. Lung is the exposure route in smoking and vaping, human lung tissue contains Cu 2+ and NADPH, and lung microsomal enzymes gave the highest rates of DNA oxidation in this study. Furthermore, E-cigarette vapor contains 6-fold more copper than that in cigarette smoke, which could exacerbate DNA oxidation.
59 BASIC BIOLOGICAL SCIENCES↗
Photolysis of Dissolved Organic Matter over Hematite Nanoplatelets
Not Available
54 ENVIRONMENTAL SCIENCES↗
Quantification of Reactive Oxygen Species Produced from Electrocatalytic Materials
Oxygen electrochemistry goes beyond O 2 , as the formation of reactive oxygen species (ROS) such as H 2 O 2 and O 3 during water oxidation is key in the destruction of persistent pollutants in water remediation technologies as well as in the degradation of fuel cell and electrolyzer components. In this study, we developed an in situ method utilizing the rotating ring-disk electrode technique to quantify the formation of O 2 , O 3 , and H 2 O 2 species across a broad pH range (1–8.3). Oxygen selectivity trends over Pt, IrO 2 , and PbO 2 surfaces reveal that even O 2 evolution catalysts may produce small yet measurable amounts of ROS, further modulated by pH and electrode potential. In conclusion, these findings emphasize the need to probe the selectivity of oxygen electrochemistry for a more complete picture of advanced materials for electrochemical technologies.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Development of Half-Sandwich Ru, Os, Rh, and Ir Complexes Bearing the Pyridine-2-ylmethanimine Bidentate Ligand Derived from 7-Chloroquinazolin-4(3H)-one with Enhanced Antiproliferative Activity
Kinesin spindle protein (KSP) inhibitors are one of the most promising anticancer agents developed in recent years. Herein, we report the synthesis of ispinesib-core pyridine derivative conjugates, which are potent KSP inhibitors, with half-sandwich complexes of ruthenium, osmium, rhodium, and iridium. Conjugation of 7-chloroquinazolin-4(3H)-one with the pyridine-2-ylmethylimine group and the organometallic moiety resulted in up to a 36-fold increased cytotoxicity with IC 50 values in the micromolar and nanomolar range also toward drug-resistant cells. All studied conjugates increased the percentage of cells in the G 2 /M phase, simultaneously decreasing the number of cells in the G 1 /G 0 phase, suggesting mitotic arrest. Additionally, ruthenium derivatives were able to generate reactive oxygen species (ROS); however, no significant influence of the organometallic moiety on KSP inhibition was observed, which suggests that conjugation of a KSP inhibitor with the organometallic moiety modulates its mechanism of action.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Species-Selective Detection of Volatile Organic Compounds by Ionic Liquid-Based Electrolyte Using Electrochemical Methods
The detection of volatile organic compounds (VOCs) is an important topic for environmental safety and public health. However, the current commercial VOC detectors suffer from cross-sensitivity and low reproducibility. In this work, we present species-selective detection for VOCs using an electrochemical cell based on ionic liquid (IL) electrolytes with features of high selectivity and reliability. The voltammograms measured with the IL-based electrolyte absorbing different VOCs exhibited species-selective features that were extracted and classified by linear discriminant analysis (LDA). The detection system could identify as many as four types of VOCs, including methanol, ethanol, acetone, formaldehyde, and additional water. A mixture of methanol and formaldehyde was detected as well. The sample required for the VOCs classification system was 50 μL, or 1.164 mmol, on average. The response time for each VOC measurement is as fast as 24 s. The volume of VOCs such as formaldehyde in solution could also be quantified by LDA and electrochemical impedance spectroscopy techniques, respectively. The system showed a tunable detection range for 1.6 and 16% (w/v) CH 2 O solution by adjusting the composition of the electrolyte. The limit of detection was as low as 1 μL. For the 1.6% CH 2 O solution, the linearity calibration range was determined to be from 5.30 to 53.00 μmol with a limit of detection at 0.53 μmol. The mechanisms for VOCs determination and quantification are also thoroughly discussed. Finally, it is expected that this work could provide a new insight into the concept of electrochemical detection of VOCs with machine learning analysis and be applied to both VOCs gas monitoring and fluid detection.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Enzymatic Routes to Designer Hemicelluloses for Use in Biobased Materials
Various enzymes can be used to modify the structure of hemicelluloses directly in vivo or following extraction from biomass sources, such as wood and agricultural residues. Generally, these enzymes can contribute to designer hemicelluloses through four main strategies: (1) enzymatic hydrolysis such as selective removal of side groups by glycoside hydrolases (GH) and carbohydrate esterases (CE), (2) enzymatic cross-linking, for instance, the selective addition of side groups by glycosyltransferases (GT) with activated sugars, (3) enzymatic polymerization by glycosynthases (GS) with activated glycosyl donors or transglycosylation, and (4) enzymatic functionalization, particularly via oxidation by carbohydrate oxidoreductases and via amination by amine transaminases. Thus, this Perspective will first highlight enzymes that play a role in regulating the degree of polymerization and side group composition of hemicelluloses, and subsequently, it will explore enzymes that enhance cross-linking capabilities and incorporate novel chemical functionalities into saccharide structures. These enzymatic routes offer a precise way to tailor the properties of hemicelluloses for specific applications in biobased materials, contributing to the development of renewable alternatives to conventional materials derived from fossil fuels.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗