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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Impacts of molecular architecture on the radiation-induced degradation and reaction kinetics of hydrophobic diglycolamides with the solvated electron and the dodecane radical cation

Given their proposed use as trivalent actinide–lanthanide separation ligands, the role of molecular architecture on the radiation robustness of diglycolamide (DGA) molecules has been investigated. This study examined three prototypical molecules with differences in their aliphatic chain architecture: N,N,N′,N′-tetra(n-octyl)diglycolamide (TODGA), N,N,N′,N′-tetra(2-ethylhexyl)diglycolamide (T2EHDGA), and N,N′-dimethyl-N,N′-dioctyldiglycolamide (DMDODGA). Rate coefficients and activation parameters are reported for the reactivity of each DGA with the solvated electron (e solv − ) and the corresponding dodecane radical cation (RH˙ + ) over the temperature range of 10.0 to 44.1 °C. These measurements indicate that DMDODGA is the most chemically reactive with both transient radicals, which may be attributed to this molecule's more accessible backbone. Complementary gamma dose accumulation studies (≤ 600 kGy) under envisioned process conditions—50 mM DGA in n-dodecane solvent—afforded dose constants for the loss of DGA of d = (3.41 ± 0.07) × 10 −3 , (4.19 ± 0.09) × 10 −3 , and (4.65 ± 0.09) × 10 −3 kGy −1 for T2EHDGA, DMDODGA, and TODGA, respectively. These dose constants indicate that varying DGA architecture affords subtle differences in chemical reactivity, leading to varying rates of radiolytic degradation under envisioned actinide–lanthanide separation conditions. However, more ambitious DGA frameworks, such as modifying the backbone, branching of the aliphatic chains, and/or changing the size of the chain may be required for larger gains in radiolytic longevity while optimizing actinide–lanthanide selectivity.

Arrhenius parameters↗
NASA NTRS1974

Individual radiosensitivity and its daily variations

The effectiveness of determining individual radiosensitivity of rats by total gas exchange measurements, studies of Na/K content in urine, and the reaction of leukocytes to intra-abdominal administration of epinephrine, was studied. The most indicative results of predicting individual reaction to radiation were obtained by the leukocyte reaction to epinephrine load; however, changes in the leukocyte content of peripheral blood after epinephrine administration depended on the initial level during the day.

Druzhinin, Y. N.↗
NASA NTRS1988

Investigation of supersonic chemically reacting and radiating channel flow

The 2-D time-dependent Navier-Stokes equations are used to investigate supersonic flows undergoing finite rate chemical reaction and radiation interaction for a hydrogen-air system. The explicit multistage finite volume technique of Jameson is used to advance the governing equations in time until convergence is achieved. The chemistry source term in the species equation is treated implicitly to alleviate the stiffness associated with fast reactions. The multidimensional radiative transfer equations for a nongray model are provided for a general configuration and then reduced for a planar geometry. Both pseudo-gray and nongray models are used to represent the absorption-emission characteristics of the participating species. The supersonic inviscid and viscous, nonreacting flows are solved by employing the finite volume technique of Jameson and the unsplit finite difference scheme of MacCormack. The specified problem considered is of the flow in a channel with a 10 deg compression-expansion ramp. The calculated results are compared with those of an upwind scheme. The problem of chemically reacting and radiating flows are solved for the flow of premixed hydrogen-air through a channel with parallel boundaries, and a channel with a compression corner. Results obtained for specific conditions indicate that the radiative interaction can have a significant influence on the entire flow field.

Mani, Mortaza↗
DOE OSTI2023

Assessing an aqueous flow cell designed for in situ crystal growth under X-ray nanotomography and effects of radiolysis products

Nucleation and growth of minerals has broad implications in the geological, environmental and materials sciences. Recent developments in fast X-ray nanotomography have enabled imaging of crystal growth in solutions in situ with a resolution of tens of nanometres, far surpassing optical microscopy. Here, a low-cost, custom-designed aqueous flow cell dedicated to the study of heterogeneous nucleation and growth of minerals in aqueous environments is shown. To gauge the effects of radiation damage from the imaging process on growth reactions, radiation-induced morphological changes of barite crystals (hundreds of nanometres to ∼1 µm) that were pre-deposited on the wall of the flow cell were investigated. Under flowing solution, minor to major crystal dissolution was observed when the tomography scan frequency was increased from every 30 min to every 5 min (with a 1 min scan duration). The production of reactive radicals from X-ray induced water radiolysis and decrease of pH close to the surface of barite are likely responsible for the observed dissolution. The flow cell shown here can possibly be adopted to study a wide range of other chemical reactions in solutions beyond crystal nucleation and growth where the combination of fast flow and fast scan can be used to mitigate the radiation effects.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Radiation-Induced Late Actinides Redox Chemistry

The goal of this proposal was to understand how radiation alters actinide redox chemistry, especially via the generation of transient oxidation states that typically cannot be isolated in bulk and need to be measured on ultrafast timescales. While these studies are of fundamental importance, they also impact the recycling of used nuclear fuel because the radiation field not only alters the oxidation states of actinides, but also induces chemical transformations of the extractants, typically in a deleterious manner. The majority of actinide radiation chemistry knowledge is concentrated toward the beginning of the series especially for uranium and plutonium, for which radiation-induced reactions have been demonstrated to significantly impact the accessibility and lifetime of actinide oxidation states at both ultrafast (pico- to microseconds) and steady-state timescales. Furthermore, there is precedence for these radiation-induced actinide redox reactions altering the radiolytic integrity of their corresponding complexes, relative to the free ligand, through facilitation of inner- versus outer-sphere reaction pathways.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
NASA NTRS2004

The Slot Gap Model for Pulsar High-Energy Emission

A new picture of pulsar high-energy emission is proposed that is different from both the traditional polar cap and outer gap models, but combines elements of each. The slot gap model is based on electron acceleration along the edge of the open field region from the neutron star surface to near the light cylinder. Along the last open field line, the pair formation front rises to very high altitude forming a slot gap, where the accelerating electric field is unscreened by pairs. Electrons continue to accelerate to high altitudes in the slot gap, reaching a radiation reaction-limited energy of several TeV. The resulting radiation pattern features sharp caustics on the trailing edge of the open field region, allowing for the possibility of double-peaked pulse profiles very similar to those observed in gamma-ray pulsars. Since emission from a large range of altitudes arrives in phase, this model very naturally explains the phase alignment of radiation at all wavelengths from the Crab pulsar.

Harding, Alice K.↗
DOE OSTI2026

Low-energy 17 O(𝑛,𝛾)⁢ 18 O reaction within the microscopic potential model and its role for the weak 𝑟 process

The neutron radiative capture reaction 17 O ⁡(𝑛,𝛾) ⁢18 O plays a pivotal role in both nuclear structure studies and astrophysical nucleosynthesis, particularly in the formation of elements during hydrostatic and explosive stellar environments. We calculated the 17 O ⁡(𝑛,𝛾) ⁢18 O cross section within the Skyrme Hartree-Fock potential model and analyzed electric dipole 𝐸⁢1 transitions to both positive- and negative-parity states below the α-decay threshold in 18 O. Our cross sections are significantly different from the data available in commonly used libraries. We further investigate the impact of the new calculated cross section on weak 𝑟-process nucleosynthesis using large-scale reaction network calculations across a wide range of electron fractions and entropies. Our results show that the 17 O ⁡(𝑛,𝛾) ⁢18 O reaction rate significantly influences the production of first 𝑟-process peak elements, such as strontium, under specific astrophysical conditions. This study highlights the importance of accurate nuclear data for light isotopes in modeling heavy-element synthesis and provides updated reaction rates for future nucleosynthesis simulations.

6 ≤ A ≤ 19↗
DOE OSTI2026

Modeling Radiolysis and Chemical Reactions during Dry Storage of Aluminum-clad Spent Nuclear Fuel

After aluminum-clad spent nuclear fuel (ASNF) is removed from the reactor, it is initially stored in spent fuel pools, which are specially designed water-filled basins that provide temporary cooling to reduce the temperature of the fuel assemblies and provide radiation shielding. ASNF continues to generate heat due to the radioactive decay of elements within the fuel, which persists for many years post-shutdown as the residual radioactive products decay into more stable elements. During the wet storage period, an oxyhydroxide layer composed of boehmite/bayerite forms on the surfaces of the aluminum cladding from exposure to water in the pools. Road-ready packaging for long-term disposition of the ASNF involves dry storage in helium backfilled DOE standard canisters (DSCs). When the ASNF is removed from water storage and dried, most of the water is removed, but some physisorbed and chemisorbed water remains in the oxyhydroxide layers. This residual water can produce hydrogen when exposed to radiation from the ASNF during dry storage. Predicting hydrogen accumulation over time in the DSCs is critical for long-term storage considerations. Previous modeling efforts have developed coupled computational fluid dynamics (CFD)-chemical models to simulate temperature, pressure, and gas phase concentrations within the DSCs. These models use the thermal field predicted by CFD as input to a radiolysis model for the gas phase and the surface oxyhydroxide layer chemistry. Given the long storage period of the DSCs and the impracticality of long-term experiments, a simulation-based approach is necessary to assess chemical evolution within the canisters. This study advances the development of a modeling framework designed to simulate the chemical evolution of spent fuel canisters. Both thermal and radiation-driven reactions are considered, with radiation kinetics quantified using G-values. Sensitivity analysis identifies key parameters influencing species composition. Reaction pathway diagrams offer insight into dominant species formation routes, enabling more effective comparisons between model predictions and experimental observations, particularly regarding the production of hydrogen. Results show that the model predicts significant hydrogen gas production with minimal oxygen generation, primarily due to hydrogen formation via boehmite pathways. These findings underscore the importance of accurately characterizing surface-bound species and radiolysis kinetics. A deeper understanding of these mechanisms is critical for evaluating the long-term safety of nuclear waste storage.

12 - MGMT OF RADIOACTIVE AND NON-RADIOACTIVE WASTE↗
DOE OSTI2026

Experimental and Multiscale Modeling Insights for Radiation-Driven Neptunium Redox Processes at Elevated Temperatures

Studies of the radiation-driven reactions of actinide elements at elevated temperatures are extremely limited, but important given that radiation heating of used nuclear fuel can affect the radiolytically promoted actinide redox processes occurring in hydroprocessing environments. Under these conditions, the high concentration of nitric acid present makes the reaction of actinides, such as neptunium, with nitric acid radiolysis products significant. Therefore, here we present derivation of the rate coefficients for the reaction of pentavalent neptunium with the nitrate radical at elevated temperature, resulting in Eyring and Arrhenius parameters for this important reaction. Here, we also revisit our previously published multiscale model predictions for radiation-induced neptunium redox chemistry and present an iteration which successfully operates over a wider range of nitric acid concentrations, 0.1–6.0 M.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
NASA NTRS1997

Data Base for CFD Validation

The flow behind the shock wave formed around objects which fly at hypervelocity behaves differently from that of a perfect gas. Molecules become vibrationally excited, dissociated, and ionized. The hot gas may emit or absorb radiation. When the atoms produced by dissociation reach the wall surface, chemical reactions, including recombination, may occur. The thermochemical phenomena of vibration, dissociation, ionization, surface chemical reaction, and radiation are referred to commonly as high-temperature real-gas phenomena. The phenomena cause changes in the dynamic behavior of the flow and the surface pressure and heat transfer distribution around the object. The character of a real gas is described by the internal degrees of freedom and state of constituent molecules; nitrogen and oxygen for air. The internal energy states, rotation, vibration and electronic, of the molecules are excited and, in the limit, the molecular bonds are exceeded and the gas dissociated into atomic and, possibly, ionic constituents. The process of energy transfer causing excitation, dissociation and recombination is a rate process controlled by particle collisions. Binary, two-body, collisions are sufficient to cause internal excitation, dissociation and ionization while three-body collisions are required to recombine the particles into molecular constituents. If the rates of energy transfer are fast with respect to the local fluid dynamic time scale the gas is in, or nearly in, equilibrium. If the energy transfer rates are very slow the gas can be described as frozen. In all other instances, wherein any of the energy exchange rates are comparable to the local fluid time scale, the gas will be thermally or chemically reacting and out of equilibrium. Real gas thermochemical nonequilibrium processes are important in the determination of aerodynamic heating; both convective (including wall catalytic effects) and radiative heating. To illustrate this we consider the hypervelocity flow over a bluff body typical of an atmospheric entry vehicle or an aerospace transfer vehicle (ASTV). The qualitative aspects of a hypersonic flow field over a bluff body are discussed in two parts, forebody and afterbody, with attention to which particular physical effects must be included in an analysis. This will indicate what type of numerical modeling will be adequate in each region of the flow. A bluff forebody flow field is dominated by the presence of the strong bow shock wave and the consequent heating, and chemical reaction of the gas. At high altitude hypersonic flight conditions the thermal excitation and chemical reaction of the gas occur slowly enough that a significant portion of the flow field is in a state of thermochemical nonequilibrium. A second important effect is the presence of the thick boundary layer along the forebody surface. In this region there are large thermal and chemical species gradients due to the interaction of the gas with the wall. Also at high altitudes the shock wave and the boundary layer may become so thick that they merge; in this case the entire shock layer is dominated by viscous effects.

Deiwert, George S.↗
DOE OSTI2024

Early-stage oxidation and subsequent damage of the used nuclear fuel extractant TODGA; electron pulse radiolysis and theoretical insights

Radiation induced damage of extractant molecules is a well-known phenomenon responsible for reducing efficiency and increasing the waste and cost of reprocessing used nuclear fuel (UNF). As such, understanding early-stage (pico- to nanoseconds) radiation-induced reaction mechanisms is essential for informing the design of next generation extractants with enhanced radiation robustness. Here, in this work, we utilized picosecond and nanosecond electron pulse radiolysis experiments to probe the early-stage radioactive environment experienced by the organic phase extractant N,N,N',N'-tetraoctyldiglycolamide (TODGA), proposed for separating highly radioactive trivalent minor actinides (specifically americium and curium) from the trivalent lanthanides. Using comparisons to the similar ionization potential (IP) solute p-xylene, this work determined the mechanism of reaction with the ionized diluent (i.e., n-dodecane radical cation, DD˙ + ) is hole transfer to produce TODGA˙ + . At high TODGA concentrations (>100 mM), the majority of this transfer occurs faster than 10 ps via the capture of DD˙ + holes prior to their solvation with a C 37 = 300 mM. The surviving solvated holes were captured with k = (2.38 ± 0.15) × 10 10 M -1 s -1 . Attempts at subsequent hole transfer to lower IP solutes found that only 10% of holes were transferred, indicating bond rupture of TODGA˙ + occurs within 2.6 ns at 200 mM TODGA. Possible reaction pathways for the rapid decomposition of TODGA˙ + were explored using a combination of experiments and density functional theory (DFT) calculations.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
NASA NTRS2015

On the Thermal Anomaly of Lake Untersee

Reported here is the outcome from a student internship undertaken with Dr. Chris McKay at the NASA Ames Research Center. The project for this internship focuses on Lake Untersee, an Earth analog for icy moons. The anoxic hole of Lake Untersee has a thermal bump that was first observed by Wand et al., 1997 and has been confirmed several times (Wand et al., 2006; Andersen 2011). The expected thermal profile of the hole is linear from 0 C at the thermocline to approximately 4 C, the ground temperature in Antarctica, at the bottom. Instead, there is an increase from 0 C near the thermocline to 5 C which is maintained for 7 m, then a linear profile to approximately 4 C near the bottom. Thermal modeling was conducted to quantify the energy input required to maintain the bump. The results revealed 2 sources. Chemical reactions and radiative energy were analyzed as possible explanation. The chemical analysis revealed a peak in Chlorophyll a at the same depth as the shallower source and several interesting reactions with maximum rates at the same location as the lower depth source. However, the energy released from these reactions was orders of magnitude smaller than required source. The radiation analysis revealed a profile with two peaks in similar locations to the sources and a total energy input within a factor of 1.5 of the required sources. The conclusion from this work is that photosynthesis and the chemical reactions support microbial life in the water column which in turn acts as an opacity to convert radiative energy into thermal energy. Recommendations for future work are aimed at quantifying the quantity and types of microbes present in the water column. Beyond the work of the project, two field trips are described and a discussion on benefits to the student of the internship is given.

Earth analog for icy moons↗
DOE OSTI2020

Radiation-Induced Catalysis of Chemical Reactions

Nuclear energy is a process which achieves zero-carbon energy and heat generation that can provide a consistent electricity load to supply the grid when renewables are not available. However, on a cost per kilowatt-hour comparison, nuclear energy is more expensive than many of the renewable energy generation technologies such as wind and solar. In order to increase the economic viability of next generation nuclear reactors for energy production, generation of a secondary product such as a chemical feedstock would increase the economic viability of nuclear energy, particularly for new installations of next-generation nuclear reactors for power production. Currently, commercial nuclear reactors are primarily used for their heat to generate steam for electricity production. There is a large amount of unused energy in the form of photon and neutron radiation that could be exploited to drive chemical processes to produce feedstock materials as a secondary product of a nuclear plant. Chemical processing with radiation is not a new concept. In fact, gamma radiation is an excellent source of high energy photons to drive photochemical reactions. Dow chemical produced commercial quantities of ethyl bromide using gamma irradiation from a 60 Co source in the 1960s and 1970s because it was the most cost-effective means of production to meet the demand.5, 6 Due to the potential economic advantages, there is a new emphasis on studying feedstock production which can be enhanced by excess gamma and neutron radiation, particularly if the reaction could be monitored in real-time which is advantageous for process optimization. A model system of lignocellulose degradation under γ- radiation was chosen for this study while following the degradation products with Raman spectroscopy in real-time.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Determining the 9 $\mathrm{Be}$($n, γ$) 10 $\mathrm{Be}$ integral cross section at fission neutron energies

The 9 B neutron capture cross section has significant implications for Be materials in the nuclear industry as well as the α process in stellar nucleosynthesis. While the cross section is well constrained at thermal neutron energies, there is a lack of experimental data at higher neutron energies, and the evaluated nuclear data libraries can differ by up to two orders of magnitude. We calculate the 9 Be(n, γ) 10 Be integral cross section at fission neutron energies in an effort to resolve disagreements amongst the nuclear data libraries. Foil irradiation experiments were performed using the Flattop critical assembly at the National Criticality Experiments Research Center with either the highly enriched U or Pu cores, with target foil stacks placed at multiple locations to exploit different neutron energy profiles. Accelerator mass spectrometry was used to measure the 10 Be/ 9 Be ratio in irradiated Be foils, while all other activation products were quantified through gamma spectrometry. The experiments were simulated using the Monte Carlo N-Particle radiation transport code and combined with experimental results to determine the total neutron fluence, while the staysl-pnnl suite and fispact-ii code were used to validate the model and assess the systematic uncertainty. The new 9 Be(n, γ) 10 Be integral cross sections calculated in this work are 26.5 ± 2.2µb at 0.59 ± 0.07 MeV, 24 ± 3 µb at 0.98 ± 0.14 MeV, 21.7 ± 1.3 µb at 1.26 ± 0.11 MeV, 21.8 ± 1.4 µb at 1.32 ± 0.11 MeV, and 18.6 ± 1.1 µb at 1.46 ± 0.13 MeV. These results do not agree with integral cross sections from any of the nuclear data library evaluations. Discrepancies between the new integral cross sections reported here and the nuclear data libraries suggest a more complex cross-section structure in the MeV range which allows for more resonance contributions, and more work is needed to further constrain the evaluated cross sections.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2026

Impact of in situ nuclear networks and atomic opacities on neutron star merger ejecta dynamics, nucleosynthesis, and kilonovae

Context. Binary neutron star merger (BNSM) ejecta are key sites of rapid neutron capture (r-process) nucleosynthesis and they produce kilonovae powered by the radioactive decay of freshly synthesized nuclei. Modeling their evolution requires multi-physics simulations involving hydrodynamics, nuclear reactions, and radiative processes. The impact of nuclear burning and atomic opacity is poorly understood and often treated with simplified prescriptions. Aims. We systematically investigate different treatments of nuclear heating, particle thermalization, and atomic opacities in radiation-hydrodynamics simulations of BNSM ejecta and kilonova light curves. Methods. Ejecta profiles from long-term numerical-relativity simulations of asymmetric neutron star binaries with a massive neutron star remnant were evolved to ∼30 days using a 2D ray-by-ray approach. We compared simplified heating-rate and thermalization prescriptions with in situ Nuclear reaction Network (NN) calculations that track nuclear energy deposition and include a composition-dependent thermalization scheme. We also contrasted various gray opacity models with a frequency-dependent treatment based on atomic calculations. Results. Coupling NN and hydrodynamics significantly affects nucleosynthesis and kilonova emission. Assuming homologous expansion alters abundance evolution and produces a narrower, less populated second r-process peak and a third peak shifted to higher mass numbers. The back-reaction of nuclear heating affects the temperature evolution enough to delay and redden the early (t∼ hours) kilonova peaks. A constant thermalization efficiency underestimates and reddens the early emission while overestimating the late-time luminosity compared to the composition-dependent treatment. Analytical opacity prescriptions yield a more extended, colder photosphere, resulting in dimmer, redder kilonovae at early times (t≲ hour), while the delayed recession of the photosphere prolongs the red emission at t ≳ 5 days. Conclusions. Coupling hydrodynamics to an in situ NN is crucial for reliable nucleosynthesis and kilonova predictions. Resolving the first several hundred milliseconds of the hydrodynamics is essential for robust nucleosynthesis calculations. Composition-dependent thermalization and frequency-dependent, atomic-physics-based opacities are needed to accurately capture the temperature evolution of the ejecta and the brightness and color evolution of the kilonova. Calibrated analytic nuclear-power fits with simplified thermalization and opacity prescriptions can still reproduce the density and temperature evolution of the ejecta.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS2005

Sulfur Oxidation and Contrail Precursor Chemistry

Sulfuric acid (H2SO4), formed in commercial aircraft operations via Fuel-S (right arrow) SO2 + SO3 (right arrow) H2SO4, plays an important role in affecting the global climate change through atmospheric chemical reactions and radiative forcing. Measurement of the sulfur oxidation rates is critical to the understanding of the contrail formation. The principle reaction pathway is SO2 + O + M (right arrow) SO3 + M. Although there are many measurements for the rates of this reaction, it has never been measured in the temperature and pressure regime available to aircraft operation. In this investigation, a series of experiments were performed behind the reflected shock waves in a shock tube. OH radicals were produced in lean, shock heated SO2/H2/O2/Ar mixtures. The reaction progress was followed using OH absorption spectroscopy at 310 nm. The data were analyzed with the aid of computer modeling/simulation. The mean value of the rate coefficients of R21 determined is k(sub 21,0)/[M]= 3.9 x 10(exp 15) cm(sup 6) per square mole per second at T = 960 - 1150 K and rho = 16-30 micromole per cubic centimeter with uncertainty limits of plus or minus 30%. A non-Arrhenius fit to our data together with all existing data gives k(sub 21,0)/[M] = 1.3 x 10(exp 24) T (exp -2.5) exp(-2350 K/T) cm(sup 6) per square mole per second at T = 300 - 2500 K with the same uncertainty limits given above. The calculated conversion of S(IV)(SO2) to S(VI) (SO3 + H2SO4) was about 2% in our experimental conditions.

DeWitt, Kenneth↗
DOE OSTI2024

Backend Nuclear Fuel Cycle Radiation Chemistry

Given global commitments to significantly increase nuclear energy capacity, it is now more important than ever to develop efficient used nuclear fuel management strategies to improve resource utilization, energy security, and waste minimization. Here, an overview of nuclear energy, backend fuel cycle challenges, and advances in used nuclear fuel reprocessing radiation chemistry will be presented. More specifically, the use of electron pulse irradiation techniques to explore radiation-induced reaction mechanisms in actinide containing solutions and solvent systems.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2023

13 C Radiofrequency Amplification by Stimulated Emission of Radiation Threshold Sensing of Chemical Reactions

Conventional nuclear magnetic resonance (NMR) enables detection of chemicals and their transformations by exciting nuclear spin ensembles with a radio-frequency pulse followed by detection of the precessing spins at their characteristic frequencies. The detected frequencies report on chemical reactions in real time and the signal amplitudes scale with concentrations of products and reactants. Here, we employ Radiofrequency Amplification by Stimulated Emission of Radiation (RASER), a quantum phenomenon producing coherent emission of 13 C signals, to detect chemical transformations. The 13 C signals are emitted by the negatively hyperpolarized biomolecules without external radio frequency pulses and without any background signal from other, nonhyperpolarized spins in the ensemble. Here, we studied the hydrolysis of hyperpolarized ethyl-[1- 13 C]acetate to hyperpolarized [1- 13 C]acetate, which was analyzed as a model system by conventional NMR and 13 C RASER. The chemical transformation of 13 C RASER-active species leads to complete and abrupt disappearance of reactant signals and delayed, abrupt reappearance of a frequency-shifted RASER signal without destroying 13 C polarization. Further, the experimentally observed “quantum” RASER threshold is supported by simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗