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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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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Antidoping in Insulators and Semiconductors Having Intermediate Bands with Trapped Carriers

Ordinary doping by electrons (holes) generally means that the Fermi level shifts towards the conduction band (valence band) and that the conductivity of free carriers increases. Recently, however, some peculiar doping characteristics were sporadically recorded in different materials without noting the mechanism: electron doping was observed to cause a portion of the lowest unoccupied band to merge into the valance band, leading to a decrease in conductivity. This behavior, that we dub as “antidoping,” was seen in rare-earth nickel oxides SmNiO 3 , cobalt oxides SrCoO 2.5 , Li-ion battery materials, and even MgO with metal vacancies. We describe the physical origin of antidoping as well as its inverse problem—the “design principles” that would enable an intelligent search of materials. We find that electron antidoping is expected in materials having preexisting trapped holes and is caused by the annihilation of such “hole polarons” via electron doping. Finally, this may offer an unconventional way of controlling conductivity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Development of Low-Intermediate Temperature Fuel Cells for Direct Conversion of Methane to Methanol Fuel

The objective of this project is development of a durable, low-cost, and high performance Low Temperature Solid Oxide Fuel Cell (LT-SOFC) for direct conversion of methane to methanol and other liquids, characterized by: a) operating temperature < 500oC, b) current density of > 100 mA/cm2 in liquid hydrocarbon production mode, c) continuous operation of > 100 h, d) cell area >100 cm2, e) cell cost per rate of product output < 100,000/bpd, f) process intensity of > 0.1 bpd/ft3, g) product yield and carbon efficiency > 50%, and h) volumetric output per cell > 30 L/day.

Torabi, Alireza↗
DOE OSTI2017

M32 analogs? A population of massive ultra-compact dwarf and compact elliptical galaxies in intermediate-redshift clusters

We report the discovery of relatively massive, M32-like ultra compact dwarf (UCD) and compact elliptical (CE) galaxy candidates in 0.2<z<0.6 massive galaxy clusters imaged by the Cluster Lensing And Supernova survey with Hubble (CLASH) survey. Examining the nearly unresolved objects in the survey, we identify a sample of compact objects concentrated around the cluster central galaxies with colors similar to cluster red sequence galaxies. Their colors and magnitudes suggest stellar masses around 10{sup 9}M{sub ⊙}. More than half of these galaxies have half-light radii smaller than 200 pc, falling into the category of massive UCDs and CEs, with properties similar to M32. The properties are consistent with a tidal stripping origin, but we cannot rule out the possibility that they are early-formed compact objects trapped in massive dark matter halos. The 17 CLASH clusters studied in this work on average contain 2.7 of these objects in their central 0.3 Mpc and 0.6 in their central 50 kpc. Our study demonstrates the possibility of statistically characterizing UCDs/CEs with a large set of uniform imaging survey data.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2018

Effect of intermediate annealing time on microstructure, texture and mechanical properties of Al-Mg-Si-Cu alloy

Highlights: • Long intermediate annealing time could be beneficial to the improvement of deep drawability. • Long intermediate annealing time could give rise to more particles with a larger average size. • As intermediate annealing time increases, strength will change and it has no positive correlation with annealing time, • A particle dissolution model is proposed to illustrate the variation of the strengths with intermediate annealing time. - Abstract: The effect of intermediate annealing time on the microstructure, texture and mechanical properties of Al-Mg-Si-Cu alloys was studied by mechanical properties, microstructure and texture characterization in the present study. The results show that the intermediate annealing time has some influence on the microstructure, recrystallization texture, and final mechanical properties. After the pre-aging treatment and natural aging treatment (T4P treatment), in contrast to the sheet with short intermediate annealing time, the sheet with long intermediate annealing time possesses higher plastic strain ratio r value. Strength has no positive correlation with annealing time, and when applying the annealing time of 16 h, the strength is highest. Before solution treatment, the sheet with long intermediate annealing time has more particles with a larger average size, compared with the sheet with short intermediate annealing time. After solution treatment, they possess the similar recrystallization equiaxed grain structure and recrystallization texture. The sheet with short intermediate annealing time is comprised of Cube{sub ND} {001} <310>, Goss {110}<001> and P {011}<122> orientations, while the sheet with long intermediate annealing time possesses weak texture including Cube{sub ND} {001}<310>, Goss {110}<001> and {015}<751> orientations. Finally, a particle dissolution model during solution treatment is proposed to explain the variation of strength with annealing time.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Nuclear Resonance Vibrational Spectroscopy Definition of O 2 Intermediates in an Extradiol Dioxygenase: Correlation to Crystallography and Reactivity

The extradiol dioxygenases are a large subclass of mononuclear nonheme Fe enzymes that catalyze the oxidative cleavage of catechols distal to their OH groups. These enzymes are important in bioremediation, and there has been significant interest in understanding how they activate O 2 . The extradiol dioxygenase homoprotocatechuate 2,3-dioxygenase (HPCD) provides an opportunity to study this process, as two O 2 intermediates have been trapped and crystallographically defined using the slow substrate 4-nitrocatechol (4NC): a side-on Fe–O 2 –4NC species and a Fe–O 2 –4NC peroxy bridged species. Also with 4NC, two solution intermediates have been trapped in the H200N variant, where H200 provides a second-sphere hydrogen bond in the wild-type enzyme. While the electronic structure of these solution intermediates has been defined previously as Fe III -superoxo-catecholate and Fe III -peroxy-semiquinone, their geometric structures are unknown. Nuclear resonance vibrational spectroscopy (NRVS) is an important tool for structural definition of nonheme Fe–O 2 intermediates, as all normal modes with Fe displacement have intensity in the NRVS spectrum. In this study, NRVS is used to define the geometric structure of the H200N–4NC solution intermediates in HPCD as an end-on Fe III -superoxo-catecholate and an end-on Fe III -hydroperoxo-semiquinone. Parallel calculations are performed to define the electronic structures and protonation states of the crystallographically defined wild-type HPCD–4NC intermediates, where the side-on intermediate is found to be a Fe III -hydroperoxo-semiquinone. The assignment of this crystallographic intermediate is validated by correlation to the NRVS data through computational removal of H200. While the side-on hydroperoxo semiquinone intermediate is computationally found to be nonreactive in peroxide bridge formation, it is isoenergetic with a superoxo catecholate species that is competent in performing this reaction. In conclusion, this study provides insight into the relative reactivities of Fe III -superoxo and Fe III -hydroperoxo intermediates in nonheme Fe enzymes and into the role H200 plays in facilitating extradiol catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Brachytherapy Improves Biochemical Failure–Free Survival in Low- and Intermediate-Risk Prostate Cancer Compared With Conventionally Fractionated External Beam Radiation Therapy: A Propensity Score Matched Analysis

Purpose: To compare, in a retrospective study, biochemical failure-free survival (bFFS) and overall survival (OS) in low-risk and intermediate-risk prostate cancer patients who received brachytherapy (BT) (either low-dose-rate brachytherapy [LDR-BT] or high-dose-rate brachytherapy with external beam radiation therapy [HDR-BT+EBRT]) versus external beam radiation therapy (EBRT) alone. Methods and Materials: Patient data were obtained from the ProCaRS database, which contains 7974 prostate cancer patients treated with primary radiation therapy at four Canadian cancer institutions from 1994 to 2010. Propensity score matching was used to obtain the following 3 matched cohorts with balanced baseline prognostic factors: (1) low-risk LDR-BT versus EBRT; (2) intermediate-risk LDR-BT versus EBRT; and (3) intermediate-risk HDR-BT+EBRT versus EBRT. Kaplan-Meier survival analysis was performed to compare differences in bFFS (primary endpoint) and OS in the 3 matched groups. Results: Propensity score matching created acceptable balance in the baseline prognostic factors in all matches. Final matches included 2 1:1 matches in the intermediate-risk cohorts, LDR-BT versus EBRT (total n=254) and HDR-BT+EBRT versus EBRT (total n=388), and one 4:1 match in the low-risk cohort (LDR-BT:EBRT, total n=400). Median follow-up ranged from 2.7 to 7.3 years for the 3 matched cohorts. Kaplan-Meier survival analysis showed that all BT treatment options were associated with statistically significant improvements in bFFS when compared with EBRT in all cohorts (intermediate-risk EBRT vs LDR-BT hazard ratio [HR] 4.58, P=.001; intermediate-risk EBRT vs HDR-BT+EBRT HR 2.08, P=.007; low-risk EBRT vs LDR-BT HR 2.90, P=.004). No significant difference in OS was found in all comparisons (intermediate-risk EBRT vs LDR-BT HR 1.27, P=.687; intermediate-risk EBRT vs HDR-BT+EBRT HR 1.55, P=.470; low-risk LDR-BT vs EBRT HR 1.41, P=.500). Conclusions: Propensity score matched analysis showed that BT options led to statistically significant improvements in bFFS in low- and intermediate-risk prostate cancer patient populations.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2015

Effect of intermediate annealing on the microstructure and mechanical property of ZK60 magnesium alloy produced by twin roll casting and hot rolling

Twin roll cast (designated as TRC in short) ZK60 magnesium alloy strip with 3.5 mm thickness was used in this paper. The TRC ZK60 strip was multi-pass rolled at different temperatures, intermediate annealing heat treatment was performed when the thickness of the strip changed from 3.5 mm to 1 mm, and then continued to be rolled until the thickness reached to 0.5 mm. The effect of intermediate annealing during rolling process on microstructure, texture and room temperature mechanical properties of TRC ZK60 strip was studied by using OM, TEM, XRD and electronic universal testing machine. The introduction of intermediate annealing can contribute to recrystallization in the ZK60 sheet which was greatly deformed, and help to reduce the stress concentration generated in the rolling process. Microstructure uniformity and mechanical properties of the ZK60 alloy sheet were also improved; in particular, the room temperature elongation was greatly improved. When the TRC ZK60 strip was rolled at 300 °C and 350 °C, the room temperature elongation of the rolled sheet with 0.5 mm thickness which was intermediate annealed during the rolling process was increased by 95% and 72% than that of no intermediate annealing, respectively. - Highlights: • Intermediate annealing was introduced during hot rolling process of twin roll cast ZK60 alloy. • Intermediate annealing can contribute to recrystallization and reduce the stress concentration in the deformed ZK60 sheet. • Microstructure uniformity and mechanical properties of the ZK60 sheet were improved, in particular, the room temperature elongation. • The elongation of the rolled ZK60 sheet after intermediate annealed was increased by 95% and 72% than that of no intermediate annealing.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Crystal structures of alkylperoxo and anhydride intermediates in an intradiol ring-cleaving dioxygenase

Intradiol aromatic ring-cleaving dioxygenases use an active site, nonheme Fe 3+ to activate O 2 and catecholic substrates for reaction. The inability of Fe 3+ to directly bind O 2 presents a mechanistic conundrum. The reaction mechanism of protocatechuate 3,4-dioxygenase is investigated in this paper using the alternative substrate 4-fluorocatechol. This substrate is found to slow the reaction at several steps throughout the mechanistic cycle, allowing the intermediates to be detected in solution studies. When the reaction was initiated in an enzyme crystal, it was found to halt at one of two intermediates depending on the pH of the surrounding solution. The X-ray crystal structure of the intermediate at pH 6.5 revealed the key alkylperoxo-Fe 3+ species, and the anhydride-Fe 3+ intermediate was found for a crystal reacted at pH 8.5. Intermediates of these types have not been structurally characterized for intradiol dioxygenases, and they validate four decades of spectroscopic, kinetic, and computational studies. In contrast to our similar in crystallo crystallographic studies of an Fe 2+ -containing extradiol dioxygenase, no evidence for a superoxo or peroxo intermediate preceding the alkylperoxo was found. This observation and the lack of spectroscopic evidence for an Fe 2+ intermediate that could bind O 2 are consistent with concerted formation of the alkylperoxo followed by Criegee rearrangement to yield the anhydride and ultimately ring-opened product. Finally, structural comparison of the alkylperoxo intermediates from the intra- and extradiol dioxygenases provides a rationale for site specificity of ring cleavage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

The physical chemistry of Criegee intermediates in the gas phase

Here, carbonyl oxides, also known as Criegee intermediates, are key intermediates in both gas phase ozonolysis of unsaturated hydrocarbons in the troposphere and solution phase organic synthesis via ozonolysis. Although the study of Criegee intermediates in both arenas has a long history, direct studies in the gas phase have only recently become possible through new methods of generating stabilised Criegee intermediates in sufficient quantities. This advance has catalysed a large number of new experimental and theoretical investigations of Criegee intermediate chemistry. In this article we review the physical chemistry of Criegee intermediates, focusing on their molecular structure, spectroscopy, unimolecular and bimolecular reactions. These recent results have overturned conclusions from some previous studies, while confirming others, and have clarified areas of investigation that will be critical targets for future studies. In addition to expanding our fundamental understanding of Criegee intermediates, the rapidly expanding knowledge base will support increasingly predictive models of their impacts on society.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Observational evidence for Criegee intermediate oligomerization reactions relevant to aerosol formation in the troposphere

Criegee intermediates are reactive intermediates that are implicated in transforming the composition of Earth’s troposphere and in the formation of secondary organic aerosol, impacting Earth’s radiation balance, air quality and human health. Yet, direct identification of their signatures in the field remains elusive. Here, from particulate and gas-phase mass-spectrometric measurements in the Amazon rainforest, we identify sequences of masses consistent with the expected signatures of oligomerization of the CH 2 OO Criegee intermediate, a process implicated in ozonolysis-driven aerosol formation. In this study, we assess the potential contributions of oligomerization through laboratory ozonolysis experiments, direct kinetic studies of Criegee intermediate reactions, and high-level theoretical calculations. Global atmospheric models built on these kinetics results indicate that Criegee intermediate chemistry may play a larger role in altering the composition of Earth’s troposphere than is captured in current atmospheric models, especially in areas of high humidity. However, the models still capture only a relatively small fraction of the observed signatures, suggesting considerable underestimates of Criegee intermediate concentrations and reactivity and/or the dominance of other, presently uncharacterized, oxidation mechanisms. Resolving the remaining uncertainties in emission inventories and the effects of atmospheric water vapour on key chemical reactions will be required to definitively assess the role of Criegee intermediate oligomerization reactions.

58 GEOSCIENCES↗
DOE OSTI2015

Perspective: Spectroscopy and kinetics of small gaseous Criegee intermediates

The Criegee intermediates, carbonyl oxides proposed by Criegee in 1949 as key intermediates in the ozonolysis of alkenes, play important roles in many aspects of atmospheric chemistry. Because direct detection of these gaseous intermediates was unavailable until recently, previous understanding of their reactions, derived from indirect experimental evidence, had great uncertainties. Recent laboratory detection of the simplest Criegee intermediate CH{sub 2}OO and some larger members, produced from ultraviolet irradiation of corresponding diiodoalkanes in O{sub 2}, with various methods such as photoionization, ultraviolet absorption, infrared absorption, and microwave spectroscopy opens a new door to improved understanding of the roles of these Criegee intermediates. Their structures and spectral parameters have been characterized; their significant zwitterionic nature is hence confirmed. CH{sub 2}OO, along with other products, has also been detected directly with microwave spectroscopy in gaseous ozonolysis reactions of ethene. The detailed kinetics of the source reaction, CH{sub 2}I + O{sub 2}, which is critical to laboratory studies of CH{sub 2}OO, are now understood satisfactorily. The kinetic investigations using direct detection identified some important atmospheric reactions, including reactions with NO{sub 2}, SO{sub 2}, water dimer, carboxylic acids, and carbonyl compounds. Efforts toward the characterization of larger Criegee intermediates and the investigation of related reactions are in progress. Some reactions of CH{sub 3}CHOO are found to depend on conformation. This perspective examines progress toward the direct spectral characterization of Criegee intermediates and investigations of the associated reaction kinetics, and indicates some unresolved problems and prospective challenges for this exciting field of research.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Nitrous oxide reduction by two partial denitrifying bacteria requires denitrification intermediates that cannot be respired

ABSTRACT Denitrification is a form of anaerobic respiration wherein nitrate (NO 3 − ) is sequentially reduced via nitrite (NO 2 − ), nitric oxide, and nitrous oxide (N 2 O) to dinitrogen gas (N 2 ) by four reductase enzymes. Partial denitrifying bacteria possess only one or some of these four reductases and use them as independent respiratory modules. However, it is unclear if partial denitrifiers sense and respond to denitrification intermediates outside of their reductase repertoire. Here, we tested the denitrifying capabilities of two purple nonsulfur bacteria,Rhodopseudomonas palustrisCGA0092 andRhodobacter capsulatusSB1003. Each had denitrifying capabilities that matched their genome annotation; CGA0092 reduced NO 2 − to N 2 , and SB1003 reduced N 2 O to N 2 . For each bacterium, N 2 O reduction could be used both for electron balance during growth on electron-rich organic compounds in light and for energy transformation via respiration in darkness. However, N 2 O reduction required supplementation with a denitrification intermediate, including those for which there was no associated denitrification enzyme. For CGA0092, NO 3 − served as a stable, non-catalyzable molecule that was sufficient to activate N 2 O reduction. Using a β-galactosidase reporter, we found that NO 3 − acted, at least in part, by stimulating N 2 O reductase gene expression. In SB1003, NO 2 − but not NO 3 − activated N 2 O reduction, but NO 2 − was slowly removed, likely by a promiscuous enzyme activity. Our findings reveal that partial denitrifiers can still be subject to regulation by denitrification intermediates that they cannot use. IMPORTANCE Denitrification is a form of microbial respiration wherein nitrate is converted via several nitrogen oxide intermediates into harmless dinitrogen gas. Partial denitrifying bacteria, which individually have some but not all denitrifying enzymes, can achieve complete denitrification as a community by cross-feeding nitrogen oxide intermediates. However, the last intermediate, nitrous oxide (N2O), is a potent greenhouse gas that often escapes, motivating efforts to understand and improve the efficiency of denitrification. Here, we found that at least some partial denitrifying N2O reducers can sense and respond to nitrogen oxide intermediates that they cannot otherwise use. The regulatory effects of nitrogen oxides on partial denitrifiers are thus an important consideration in understanding and applying denitrifying bacterial communities to combat greenhouse gas emissions.

Biotechnology & Applied Microbiology↗
DOE OSTI2017

Measuring, Cutting and Sorting Irradiated Control Rods to Limit the Volume of Intermediate Level Long-lived Waste - 17001

During operation, the PWR control rods are either completely extracted (scram or safety rods) or partially inserted in the operating zone of the core (fine control or operating rods). At the nominal rating conditions or close to them, the operating zone is limited to some steps of insertion in the order of a few tens of cm. In fact, only the lower part of the control rods are subjected to a significant neutron flux with an impact on the neutron activation and so on the waste classification (Low Level Short-lived Waste versus Intermediate Level Long-lived Waste). Our calculative as well as experimental experience confirms the significant presence of radionuclides in the control rods, but only in the lower parts. Measuring, cutting and finally sorting control rod scraps can reduce the volume of Intermediate Level Long-lived Waste planned for our storage deposit facility. This paper presents the EDF/DP2D methodologies followed to determine the sort criteria between the Low Level Short-lived Waste versus the Intermediate Level Long-lived Waste zones for the Silver-Indium-Cadmium control rods. The irradiated control rods are stored in cases without their head. Each case can contain several control rods, and the cases are stored under water in the fuel assembly pool. To calculate the radioactive inventories, we have developed a calculation scheme which is composed of a 3-dimensional mapping of the neutron flux, a calculation of the evolution of the isotopic compositions under neutron flux and finally a comparison between calculated and measured values. The main hypotheses of the control rods calculation take into account: - 3-dimensional geometry and 3-dimensional neutron sources distribution, - the isotopic compositions including impurities, - the history of irradiation resulting mainly from the daily power production, the positions of the control rods in the loading patterns and the positions in the axial operating zone. In order to validate the calculations, measurements were made 20 meters under water in the fuel assembly pool. The experimental results show the presence of many gamma emitter radionuclides. Only Ag-108m was retained for validating the calculations. This is due to the fact that silver is considered as the 'standard' chemical element for our control rods and silver produces Ag-108m which is a long-lived gamma emitter radionuclide. The analysis of the calculated results and the measured values allow us to build a simplified physics model for the simulation of the control rods activation. Finally three sort criteria can be proposed: - Without measurement devices, the sorting is based on an empirical sort criterion. Cuttings must then be made on the 2 back-ends of the control rod pins. This option is due to the difficulty in knowing the orientation of the pins in the storage cases. The cutting lines are placed at approximately 1 m from the 2 back-ends of the pins. This approach does not allow a great optimization of the sorting, less than 50% of the length of the control rods can be saved from Intermediate Level Long-lived Waste storage. - With a simple dose rate measurement device, the knowledge of the orientation of the pins in the storage cases allows us to limit cuttings to the lower part of the control rods. Depending on the 'top to tail' cases, between approximately 50% and 75% of the length of the control rods can be saved from Intermediate Level Long-lived Waste storage. - With an accurate measurement device, the sorting can be based on a specific activity of Ag-108m. Over 4400 Bq/g of Ag-108m (corresponding to the Intermediate Level Long-lived Waste limit), the control rod pieces can be considered as a long-lived waste. The measurements must be made over the 2 back-ends of control rod pins to examine the cases of 'top to tail' storage. This approach allows a great optimization of the sorting. Depending on the history of irradiation, more than 75% of the length of the control rods can be saved from Intermediate Level Long-lived Waste storage. (author)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Long G2 accumulates recombination intermediates and disturbs chromosome segregation at dysfunction telomere in Schizosaccharomyces pombe

Protection of telomere (Pot1) is a single-stranded telomere binding protein which is essential for chromosome ends protection. Fission yeast Rqh1 is a member of RecQ helicases family which has essential roles in the maintenance of genomic stability and regulation of homologous recombination. Double mutant between fission yeast pot1Δ and rqh1 helicase dead (rqh1-hd) maintains telomere by homologous recombination. In pot1Δ rqh1-hd double mutant, recombination intermediates accumulate near telomere which disturb chromosome segregation and make cells sensitive to microtubule inhibitors thiabendazole (TBZ). Deletion of chk1{sup +} or mutation of its kinase domain shortens the G2 of pot1Δ rqh1-hd double mutant and suppresses both the accumulation of recombination intermediates and the TBZ sensitivity of that double mutant. In this study, we asked whether the long G2 is the reason for the TBZ sensitivity of pot1Δ rqh1-hd double mutant. We found that shortening the G2 of pot1Δ rqh1-hd double mutant by additional mutations of wee1 and mik1 or gain of function mutation of Cdc2 suppresses both the accumulation of recombination intermediates and the TBZ sensitivity of pot1Δ rqh1-hd double mutant. Our results suggest that long G2 of pot1Δ rqh1-hd double mutant may allow time for the accumulation of recombination intermediates which disturb chromosome segregation and make cells sensitive to TBZ. - Ηighlights: • We show link between long G2 and accumulation of toxic recombination intermediates. • Accumulation of recombination intermediates at telomere results in TBZ sensitivity. • Activation of DNA damage checkpoint worsens cells' viability in presence of TBZ.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2017

Low-Dose-Rate Brachytherapy Versus Cryotherapy in Low- and Intermediate-Risk Prostate Cancer

Purpose: Cryotherapy and brachytherapy are definitive local treatment options for low- to intermediate-risk prostate cancer. There are both prospective and retrospective data for brachytherapy, but the use of cryotherapy has been limited primarily to single-institution retrospective studies. Currently, no published evidence has compared low-dose-rate brachytherapy versus cryotherapy. Methods and Materials: Institutional review board approval was obtained to conduct a retrospective chart review of consecutive patients treated at our institution from 1990 to 2012. For inclusion, patients must have received a prostate cancer diagnosis and have been considered to have low- to intermediate-risk disease according to the National Comprehensive Cancer Network criteria. All patients received brachytherapy or cryotherapy treatment. Disease specifics and failure details were collected for all patients. Failure was defined as prostate-specific antigen nadir +2 ng/mL. Results: A total of 359 patients were analyzed. The groups comprised 50 low-risk cryotherapy (LRC), 92 intermediate-risk cryotherapy (IRC), 133 low-risk brachytherapy (LRB), and 84 intermediate-risk brachytherapy (IRB) patients. The median prostate-specific antigen follow-up periods were 85.6 months (LRC), 59.2 months (IRC), 74.9 months (LRB), and 59.8 months (IRB). The 5-year biochemical progression–free survival (bPFS) rate was 57.9% in the cryotherapy group versus 89.6% in the brachytherapy group (P<.0001). The 5-year bPFS rate was 70.0% (LRC), 51.4% (IRC), 89.4% (LRB), and 89.7% (IRB). The bPFS rate was significantly different between brachytherapy and cryotherapy for low- and intermediate-risk groups (P<.05). The mean nadir temperature reached for cryotherapy patients was −35°C (range, −96°C to −6°C). Cryotherapy used a median of 2 freeze-thaw cycles (range, 2-4 freeze-thaw cycles). Conclusions: Results from this study suggest that cryotherapy is inferior to brachytherapy for patients with low- to intermediate-risk prostate cancer. Patient selection criteria for consideration of cryotherapy and brachytherapy are similar in terms of anesthesia candidacy. Therefore, cryotherapy would not be recommended as a first-line local therapy for this particular patient subset.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2017

Photoinduced Reductive Elimination of H 2 from the Nitrogenase Dihydride (Janus) State Involves a FeMo-cofactor-H 2 Intermediate

N 2 reduction by nitrogenase involves the accumulation of four reducing equivalents at the active site FeMo-cofactor to form a state with two [Fe-H-Fe] bridging hydrides (denoted E 4 (4H), the Janus intermediate), and we recently demonstrated that the enzyme is activated to cleave the N≡N triple bond by the reductive elimination (re) of H 2 from this state. We are exploring a photochemical approach to obtaining atomic-level details of the re activation process. We have shown that when E 4 (4H) at cryogenic temperatures is subjected to 450 nm irradiation in an EPR cavity, it cleanly undergoes photoinduced re of H 2 to give a reactive doubly-reduced intermediate, denoted E4(2H)*, which corresponds to the intermediate that would form if thermal dissociative re loss of H 2 preceded N 2 binding. Experiments reported here establish that photoinduced re occurs in two steps. Photolysis of E 4 (4H) generates an intermediate state that undergoes subsequent photoinduced conversion to [E 4 (2H)* + H 2 ]. The experiments, supported by DFT calculation, indicate that the trapped intermediate is an H 2 complex on the ground adiabatic potential energy suface that connects E 4 (4H) with [E 4 (2H)* + H 2 ]. We suggest this complex, denoted E 4 (H 2 ; 2H), is a thermally populated intermediate in the catalytically central re of H 2 by E 4 (4H), and that N 2 reacts with this complex to complete the activated conversion of [E 4 (4H) + N2] into [E 4 (2N2H) + H 2 ].

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Direct Observation of Solvent–Reaction Intermediate Interactions in Heterogeneously Catalyzed Alcohol Coupling

The relative stability of reactive intermediates and reactants on a surface, which dictates the rate and selectivity of catalytic reactions in both gas and liquid phases, is dependent on numerous factors. One well-established example is secondary interactions, such as van der Waals interactions between the catalyst surface and the pendant group of the intermediate, which can govern reaction selectivity for coupling reactions. In this work, we directly show that interactions between adsorbed reaction intermediates and reactant molecules increase the binding energy and affects the geometrical arrangement of coadsorbed reactant/solvent molecules. Evidence for this effect is demonstrated for the oxidative coupling reaction of methanol on a single crystal gold (Au(110)) surface. The rate-limiting reaction intermediate for methanol selfcoupling, methoxy, stabilizes excess adsorbed methanol, which desorbs as a result of beta-hydride decomposition of the adsorbed methoxy. Direct molecular-scale imaging by scanning tunneling microscopy, supplemented by density functional theory, revealed interactive structures formed by methoxy and coadsorbed methanol. Interactions between the methoxy intermediate and coadsorbed methanol stabilizes a hydrogen-bonded network comprising methoxy and methanol by a minimum of 0.13 eV per methanol molecule. Inclusion of such interactions between reaction intermediates and coadsorbed reactants and solvents in kinetic models is important for microkinetic analysis of the rates and selectivities of catalytic reactions in both the gas and liquid phases whenever appreciable coverages of species from the ambient phase exist.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

In Situ Structural Observation of a Substrate- and Peroxide-Bound High-Spin Ferric-Hydroperoxo Intermediate in the P450 Enzyme CYP121

The P450 enzyme CYP121 from Mycobacterium tuberculosis catalyzes a carbon–carbon (C–C) bond coupling cyclization of the dityrosine substrate containing a diketopiperazine ring, cyclo(l-tyrosine-l-tyrosine) (cYY). An unusual high-spin (S = 5/2) ferric intermediate maximizes its population in less than 5 ms in the rapid freeze-quenching study of CYP121 during the shunt reaction with peracetic acid or hydrogen peroxide in acetic acid solution. Here, we show that this intermediate can also be observed in the crystalline state by EPR spectroscopy. By developing an on-demand-rapid-mixing method for time-resolved serial femtosecond crystallography with X-ray free-electron laser (tr-SFX-XFEL) technology covering the millisecond time domain and without freezing, we structurally monitored the reaction in situ at room temperature. After a 200 ms peracetic acid reaction with the cocrystallized enzyme–substrate microcrystal slurry, a ferric-hydroperoxo intermediate is observed, and its structure is determined at 1.85 Å resolution. The structure shows a hydroperoxyl ligand between the heme and the native substrate, cYY. The oxygen atoms of the hydroperoxo are 2.5 and 3.2 Å from the iron ion. The end-on binding ligand adopts a near-side-on geometry and is weakly associated with the iron ion, causing the unusual high-spin state. This compound 0 intermediate, spectroscopically and structurally observed during the catalytic shunt pathway, reveals a unique binding mode that deviates from the end-on compound 0 intermediates in other heme enzymes. The hydroperoxyl ligand is only 2.9 Å from the bound cYY, suggesting an active oxidant role of the intermediate for direct substrate oxidation in the nonhydroxylation C–C bond coupling chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗