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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

Trace double-component gas sensor in photoacoustic spectroscopy based on frequency division multiplexing

In this paper, we demonstrated a trace double-component gas detection system based on frequency division multiplexing using two-way distributed feedback laser diode (DFB-LD) as the excitation laser source. In the frequency response range of photoacoustic spectroscopy (PAS) cell, this detection system could detect the second harmonics of different frequencies f{sub 0} and f{sub 1}, which were excited by the gas absorption using the two wavelengths of DFB-LD at modulation frequencies f{sub 0}/2 and f{sub 1}/2. Unlike previous double-component gas sensor, these two DFB-LDs connected into the both ends of PAS cell without optical fiber coupler could effectively improve the excited light intensity and simplify the system structure. This feature allowed the trace detection of double-component gas of mixed-methane (CH{sub 4}) and water (H{sub 2}O) vapor with a low detection limits 11.055 ppm and 885 ppb, respectively. Additionally, the linear responses to the gas concentration were achieved 0.9986 and 0.9997, and it exhibited potentially as an effective detection system for complex gas component.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2019

Pyrrolizidine Alkaloids-Free Extract from the Cell Culture of Lithospermum officinale with High Antioxidant Capacity

The benefits of Lithospermum officinale has encouraged people to continue using its extract (CAS 90063-58-4) in both medicinal and cosmetic industries despite the fact that chemical analysis confirms the presence of pyrrolizidine alkaloids (PAs) in the extract. While the cultivation of L. officinale takes, at least, 2 years to produce usable crops, its callus culture proliferated 8.3 times with 4.9-fold biomass in less than 30 days under the applied conditions in this study. Under the applied conditions, the cell extract contained no toxic PAs while phenylpropanoid pathway was active toward phenolic acids formation not toward naphthoquinone derivatives. Rosmarinic acid was produced as the main constituent. Total phenolic content and antioxidant capacity of the proliferated cell extracts were similar to those of the extracts of the natural plant tissues, in particular from the root. These results support the idea that the extract of L. officinale cells can be a reliable substitute for the extract of the natural plant tissues.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2016

Use of phosphoranimines to reduce organic carbonate content in Li-ion battery electrolytes

In this study, the use of phosphoranimines (PAs), a class of linear, monomeric phosphazenes, as electrolytes for Li-ion battery applications has been investigated as a route to improve safety and stability for Li-ion batteries. Of the potential PAs for use in battery applications, this work focuses on the initial synthetic preparation and analysis of N-trimethylsilyl-P,P-bis((2-methoxyethoxy)ethoxy)-P-ethylphosphoranimine (PA-5). PA-5 has high LiPF6 solubility in excess of 2 M, high thermal stability with a melting point below -80°C and high thermal stability as a neat compound to at least 250°C. As part of electrolyte blends, the inclusion of PA-5 shifts the onset of thermal degradation by close to 40°C at 35% loading and by 20°C at a 10% loading, improves the low temperature performance of the electrolyte, and when used as a primary solvent leads to increases in the flash point (by 20°C) when compared to more traditional EC:EMC blends. Cycling capabilities of full-coin cells with graphite negative electrodes and Li 1+w [Ni 0.5 Mn 0.3 Co 0.2 ] 1-w O 2 positive electrodes using PA-5:EC:EMC electrolyte blends are comparable with the performance seen for traditional EC:EMC blends. Analysis of the impact of the use of additives such as vinylene carbonate in PA-5:EC:EMC blended electrolyte results in enhanced capacity retention and improved coulombic efficiency.

25 ENERGY STORAGE↗
DOE OSTI2022

Effect of rhenium addition on deuterium retention in neutron-irradiated tungsten

In this work, the effects of rhenium (Re) addition on deuterium (D) retention in neutron-irradiated tungsten (W) were investigated. Pure W and W-5Re (5 at.%) alloy samples were irradiated with neutrons at High Flux Isotope Reactor using MFE-RB-19 J capsule. The sample temperature and the damage level were 864 K and 0.35 dpa for pure W and 792 K and 0.26 dpa for W-5Re alloy. A portion of the samples was exposed to D plasma at Tritium Plasma Experiment at Idaho National Laboratory at 823 K to a fluence of 5 × 1025 m -2 . Vacancy-type defects in neutron-irradiated samples were examined using positron annihilation spectroscopy (PAS); D retention after plasma exposure was evaluated by thermal desorption spectrometry (TDS). TDS measurements revealed that D retention in the neutron-irradiated W-5Re alloy was similar to that in the unirradiated W sample, whereas a significant increase in D retention was observed in neutron-irradiated W. Thus, Re addition significantly suppressed the increase in D retention after neutron irradiation. This effect was attributed to the suppression of vacancy-type defect formation, as confirmed by PAS.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Controlling Heterogeneous Catalysis with Organic Monolayers on Metal Oxides

A key theme of heterogeneous catalysis research is achieving control of the environment surrounding the active site to precisely steer the reactivity toward desired reaction products. One method toward this goal has been the use of organic ligands or self-assembled monolayers (SAMs) on metal nanoparticles. Metal-bound SAMs are typically employed to improve catalyst selectivity but often decrease the reaction rate as a result of site blocking from the ligands. Recently, the use of metal oxide-bound organic modifiers such as organophosphonic acid (PA) SAMs has shown promise as an additional method for tuning reactions on metal oxide surfaces as well as modifying oxide-supported metal catalysts. In this Account, we summarize recent approaches to enhance catalyst performance with oxide-bound monolayers. These approaches include (1) modification of metal oxide catalysts to tune surface reactions, (2) formation of SAMs on the oxide component of supported metal catalysts to modify sites at the metal–support interface, and (3) enhancement of catalyst performance (e.g., stability) through modification of sites remote from the active sites. Further, both the headgroups and organic tail groups of PA SAMs or other ligands can influence reactions on metal oxide surfaces. Binding of the headgroup can selectively poison certain active sites, altering the selectivity in a manner analogous to metal-bound ligands (at the expense of active site quantity). Moreover, tail groups can be functionalized to interact favorably with reactants and intermediates, for instance through dipole–dipole interactions. On supported metal catalysts like Pt/Al 2 O 3 , PA SAMs can selectively form on the oxide support. This selective deposition allows for modification of the metal–support interface with minimal blockage of metal sites. PA headgroups were shown to provide tunable acid sites at the interface, dramatically improving hydrodeoxygenation rates of various alcohols. Additionally, organic tail functionality was used to activate or stabilize specific reactants at the interface, such as with the use of amine-functionalized PAs to stabilize chemisorption of CO 2 during the reverse water gas shift reaction. PAs have also been found to affect the electronic properties of bulk metal sites through long-range electron withdrawal via the oxide, providing an additional avenue to tune catalytic behavior. Finally, organic modifiers were shown to enhance catalytic performance without directly modifying the active site. For instance, in biphasic liquid environments the modification of catalyst particles with hydrophobic or hydrophilic SAMs shifts the selectivity of multipath reactions on the basis of the hydrophobicities of different intermediates and products. As another “long-range” effect, the deposition of ligands on oxide supports improved catalyst stability through both improved resistance to sintering and suppression of active site poisoning. The recent contributions discussed in this Account demonstrate the versatility and significant potential for the approach of modifying catalysts with oxide-bound organic monolayers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Structural Insights into Mycobacterium tuberculosis Rv2671 Protein as a Dihydrofolate Reductase Functional Analogue Contributing to para -Aminosalicylic Acid Resistance

Mycobacterium tuberculosis ( Mtb ) Rv2671 is annotated as a 5-amino-6-ribitylamino-2,4(1 H ,3 H )-pyrimidinedione 5'-phosphate (AROPP) reductase (RibD) in the riboflavin biosynthetic pathway. Recently, a strain of Mtb with a mutation in the 5' untranslated region of Rv2671 , which resulted in its overexpression, was found to be resistant to dihydrofolate reductase (DHFR) inhibitors including the anti- Mtb drug para-aminosalicylic acid (PAS). In this study, a biochemical analysis of Rv2671 showed that it was able to catalyze the reduction of dihydrofolate (DHF) to tetrahydrofolate (THF), which explained why the overexpression of Rv2671 was sufficient to confer PAS resistance. We solved the structure of Rv2671 in complex with the NADP + and tetrahydrofolate (THF), which revealed the structural basis for the DHFR activity. Furthermore, the structures of Rv2671 complexed with two DHFR inhibitors, trimethoprim and trimetrexate, provided additional details of the substrate binding pocket and elucidated the differences between their inhibitory activities. Finally, Rv2671 was unable to catalyze the reduction of AROPP, which indicated that Rv2671 and its closely related orthologues are not involved in riboflavin biosynthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Enhancing Au/TiO 2 Catalyst Thermostability and Coking Resistance with Alkyl Phosphonic-Acid Self-Assembled Monolayers

Metal oxide-supported Au catalysts, particularly those with small Au nanoparticles, catalyze a variety of reactions including low-temperature CO oxidation and selective hydrogenation of alkynes. However, the facile nature of Au particle growth at even moderate temperatures poses significant challenges to maintaining catalyst activity under reaction conditions. In this paper, we present a method to reduce the rate of sintering and coke formation in TiO 2 -supported Au catalysts via the deposition of alkyl-phosphonic acid (PA) self-assembled monolayers. After surface modification with PAs, the resultant catalysts exhibited significantly improved resistance to Au sintering. PA deposition strongly suppressed CO oxidation rates, consistent with poisoning of active sites. In contrast, modification with PAs significantly improved the rate of C 2 H 2 hydrogenation on Au/TiO 2 . The enhanced activity was accompanied by a dramatically improved resistance to accumulation of surface carbonaceous species.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Effects of Phosphonic Acid Monolayers on the Dehydration Mechanism of Aliphatic Alcohols on TiO 2

The kinetics for surface-catalyzed alcohol dehydration reactions often depend on the structure of the alcohol. Studies of structure–activity relations across primary, secondary, and tertiary alcohols can provide fundamental information on the nature of active sites on the surface. Here in this paper, we investigated the dehydration of 1-butanol, 2-butanol, and tert-butanol over TiO 2 anatase catalysts modified with various phosphonic acid (PA) self-assembled monolayers (SAMs). As a response to the presence of PAs, the three C4 alcohol isomers showed different dehydration rates, with 1-butanol dehydration being enhanced to the greatest extent by PA modification. Furthermore, the fluorinated, more polar 4-fluorobenzylphosphonic acid outperformed alkyl PAs across all alcohols. Steady-state kinetic measurements and temperature-programmed desorption studies indicated that PA SAMs significantly lowered the dehydration activation barrier; the extent of reduction in the barrier was sensitive to both the substitution of the alcohol and the charge distribution on the PA in a way that was consistent with stabilization of a carbenium-like transition state. Overall, the effect of PA modifiers on alcohol dehydration rates was found to be determined from a balance between transition state stabilization and active site blocking effects, with the potential to tune activity and selectivity based on the structure and coverage of the SAM.

09 BIOMASS FUELS↗
DOE OSTI2014

Light-Controlled Hierarchical Self-Assembly of Polyelectrolytes and Supramolecular Polymers

Dynamic control over supramolecular interactions using various stimuli continues to drive the development of smart materials. In this paper, we describe the extension of dynamic self-assembly to a self-assembled hierarchical structure. A peptide amphiphile (PA) was designed with a photocleavable nitrobenzyl ester component such that it would undergo a sphere-to-cylinder transition upon irradiation, as confirmed by cryogenic transmission electron microscopy and small-angle X-ray scattering (SAXS). The photocleavable PA was then tested in the formation of a macroscopic sac made through a complex hierarchical self-assembly process between PA and hyaluronic acid. The microstructure of the resulting sac has previously been noted to depend dramatically on the geometry of the PA nanostructure. Photolysis of the PA solution during sac formation led to a sac microstructure that displayed characteristics of sacs made with both cylinder-forming PAs and sphere-forming PAs, as measured by scanning electron microscopy and SAXS.

36 MATERIALS SCIENCE↗
DOE OSTI2024

The role of interfacial donor–acceptor percolation in efficient and stable all-polymer solar cells

Polymerization of Y6-type acceptor molecules leads to bulk-heterojunction organic solar cells with both high power-conversion efficiency and device stability, but the underlying mechanism remains unclear. Here we show that the exciton recombination dynamics of polymerized Y6-type acceptors (Y6-PAs) strongly depends on the degree of aggregation. While the fast exciton recombination rate in aggregated Y6-PA competes with electron-hole separation at the donor–acceptor (D–A) interface, the much-suppressed exciton recombination rate in dispersed Y6-PA is sufficient to allow efficient free charge generation. Indeed, our experimental results and theoretical simulations reveal that Y6-PAs have larger miscibility with the donor polymer than Y6-type small molecular acceptors, leading to D–A percolation that effectively prevents the formation of Y6-PA aggregates at the interface. Besides enabling high charge generation efficiency, the interfacial D–A percolation also improves the thermodynamic stability of the blend morphology, as evident by the reduced device “burn-in” loss upon solar illumination.

14 SOLAR ENERGY↗
DOE OSTI2019

Bidirectional modulation of HIF-2 activity through chemical ligands

Hypoxia-inducible factor-2 (HIF-2) is a heterodimeric transcription factor formed through dimerization between an oxygen-sensitive HIF-2 alpha subunit and its obligate partner subunit ARNT. Enhanced HIF-2 activity drives some cancers, whereas reduced activity causes anemia in chronic kidney disease. Therefore, modulation of HIF-2 activity via direct-binding ligands could provide many new therapeutic benefits. Here, we explored HIF-2 alpha chemical ligands using combined crystallographic, biophysical, and cell-based functional studies. We found chemically unrelated antagonists to employ the same mechanism of action. Their binding displaced residue M252 from inside the HIF-2 alpha PAS-B pocket toward the ARNT subunit to weaken heterodimerization. We also identified first-in-class HIF-2 alpha agonists and found that they significantly displaced pocket residue Y281. Its dramatic side chain movement increases heterodimerization stability and transcriptional activity. Our findings show that despite binding to the same HIF-2 alpha PAS-B pocket, ligands can manifest as inhibitors versus activators by mobilizing different pocket residues to allosterically alter HIF-2 alpha-ARNT heterodimerization.

Wu, Dalei↗
DOE OSTI2022

Investigating Deposition Sequence During Synthesis of Pd/Al2O3 Catalysts Modified with Organic Monolayers

Modification of supported metal catalysts with self-assembled monolayers (SAMs) has been shown to improve selectivity and turnover frequencies (TOFs) for many catalytic reactions. However, these benefits are often accompanied by a decrease in overall mass activity due to partial blocking of active sites by the monolayers. Therefore, a potential method for increasing site accessibility is to deposit the active metal (e.g., Pd) after deposition of a SAM modifier on the support material. In this work, Pd/Al2O3 catalysts were synthesized using both a conventional, "metal-first" sequence in which the phosphonic acid (PA) SAM was deposited on Pd/Al2O3 and a "SAM-first" technique in which the ligands were deposited onto the support prior to deposition of the metal. Although metal-first catalysts showed a significant increase in TOF during benzyl alcohol HDO, they exhibited only a modest increase in overall mass activity due to a decrease in the number of active sites. Meanwhile, SAM-first catalysts showed similar improvements in TOF and toluene selectivity but exhibited significantly improved HDO rates compared to metal-first catalysts. The rate increase was attributed to reduced site blocking as evidenced by CO chemisorption measurements. Additionally, analysis of catalysts having high Pd loadings using transmission electron microscopy (TEM) showed that SAM-first catalysts generally resulted in lower average particle sizes than traditionally modified and unmodified catalysts, suggesting that precoating the support surface with PAs changes the way that Pd is deposited during incipient wetness, leading here to improved activity.

catalytic reactions↗
DOE OSTI2014

Understanding the presence of vacancy clusters in ZnO from a kinetic perspective

Vacancy clusters have been observed in ZnO, but their physical origin remains elusive. This is because under thermal equilibrium clusters typically have higher formation energies. Combining first-principles calculation and kinetic Monte Carlo (kMC) simulation, we determine the roles of non-equilibrium kinetics on the vacancy clustering. We find that clustering starts with the formation of Zn and O vacancy pairs (VZn-Vo), which further grow by attracting additional mono-vacancies. At this stage, vacancy diffusivity becomes crucial: due to the larger diffusivity of VZn compared to VO, more VZn-abundant clusters are formed than VO-abundant clusters. The large dissociation energies, e.g., 3 eV for (VZn-Vo), suggest that, once formed, it is difficult for the clusters to dissociate. As such, thermal annealing will increase the size of the clusters by promoting mono-vacancy diffusion, in agreement with experiment.

Ab initio calculations↗
DOE OSTI2021

Gallium vacancy formation in oxygen annealed β-Ga 2 O 3

Here, the formation and character of gallium vacancies (V Ga ) and their complexes in near surface and bulk regions of single crystal β-Ga 2 O 3 were explored using unintentionally doped single crystals grown by the Czochralski method. As-grown and O 2 annealed (up to 1550 °C) samples were investigated using positron annihilation spectroscopy (PAS) to study the top 0.05–6 μm, and also current–voltage measurements and infrared (IR) spectroscopy, with hydrogenated samples to probe V Ga , to study the bulk. After annealing in O 2 > 1000 °C, the β-Ga 2 O 3 resistivity begins increasing, up to ~10 9 Ω cm for 1550 °C treatment, with the top 0.5 mm being many orders of magnitude more resistive. PAS measurements of the top 6 μm (S values) and very near surface 200 nm (diffusion length, L) indicate differential behavior as a function of peak annealing temperature. At least four temperature regimes of behavior are described. V Ga are present in the bulk after growth, but considerable changes occur upon annealing at a temperature ≈1000 °C, where L and S decrease simultaneously, suggesting an increasing defect concentration (L) but a decreasing defect volume (S). Annealing at a temperature ≈1400 °C increases S again, showing an increasing volume concentration of V Ga , with IR absorption showing a large signature of V Ga -2H, indicative of increased V Ga formation that was not present when annealing at a temperature ≈1000 °C. These results suggest that defect changes from annealing in oxygen are depth dependent, and that V Ga configuration may not be the same near the oxygen-exposed surface of the sample and in the bulk.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2017

Structural hierarchy controlling dimerization and target DNA recognition in the AHR transcriptional complex

The aryl hydrocarbon receptor (AHR) belongs to the PAS (PER-ARNT-SIM) family transcription factors and mediates broad responses to numerous environmental pollutants and cellular metabolites, modulating diverse biological processes from adaptive metabolism, acute toxicity, to normal physiology of vascular and immune systems. The AHR forms a transcriptionally active heterodimer with ARNT (AHR nuclear translocator), which recognizes the dioxin response element (DRE) in the promoter of downstream genes. We determined the crystal structure of the mammalian AHR–ARNT heterodimer in complex with the DRE, in which ARNT curls around AHR into a highly intertwined asymmetric architecture, with extensive heterodimerization interfaces and AHR interdomain interactions. Specific recognition of the DRE is determined locally by the DNA-binding residues, which discriminates it from the closely related hypoxia response element (HRE), and is globally affected by the dimerization interfaces and interdomain interactions. Changes at the interdomain interactions caused either AHR constitutive nuclear localization or failure to translocate to nucleus, underlying an allosteric structural pathway for mediating ligand-induced exposure of nuclear localization signal. Furthermore, these observations, together with the global higher flexibility of the AHR PAS-A and its loosely packed structural elements, suggest a dynamic structural hierarchy for complex scenarios of AHR activation induced by its diverse ligands.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2015

The shape of LITTLE THINGS dwarf galaxies DDO 46 and DDO 168: Understanding the stellar and gas kinematics

Determining the shape of dwarf irregular (dIrr) galaxies is controversial because if one assumes that these objects are disks and if these disks are randomly distributed over the sky, then their projected minor-to-major axis ratios should follow a particular statistical distribution, which is not observed. Thus, different studies have led to different conclusions. Some believe that the observed distributions can be explained by assuming the dIrrs are thick disks while others have concluded that dIrrs are triaxial. Fortunately, the central stellar velocity dispersion, σ{sub z,0}, combined with maximum rotation speed, V{sub max}, provides a kinematic measure, V{sub max}/σ{sub z,0}, which gives the three-dimensional shape of a system. In this work, we present the stellar and gas kinematics of DDO 46 and DDO 168 from the Local Irregulars That Trace Luminosity Extremes; The H i Nearby Galaxy Survey (LITTLE THINGS) and determine their respective V{sub max}/σ{sub z,0} values. We used the Kitt Peak National Observatory's Mayall 4 m telescope with the Echelle spectrograph as a long-slit spectrograph, which provided a two-dimensional, 3′-long slit. We acquired spectra of DDO 168 along four position angles (PAs) by placing the slit over the morphological major and minor axes and two intermediate PAs. However, due to poor weather conditions during our observing run for DDO 46, we were able to extract only one useful data point from the morphological major axis. We determined a central stellar velocity dispersion perpendicular to the disk, σ{sub z,0}, of 13.5 ± 8 km s{sup −1} for DDO 46 and 〈σ{sub z,0}〉 of 10.7 ± 2.9 km s{sup −1} for DDO 168. We then derived the maximum rotation speed in both galaxies using the LITTLE THINGS H i data. We separated bulk motions from non-circular motions using a double Gaussian decomposition technique and applied a tilted-ring model to the bulk velocity field. We corrected the observed H i rotation speeds for asymmetric drift and found a maximum velocity, V{sub max}, of 77.4 ± 3.7 and 67.4 ± 4.0 for DDO 46 and DDO 168, respectively. Thus, we derived a kinematic measure, V{sub max}/σ{sub z,0}, of 5.7 ± 0.6 for DDO 46 and 6.3 ± 0.3 for DDO 168. Comparing these values to ones determined for spiral galaxies, we find that DDO 46 and DDO 168 have V{sub max}/σ{sub z,0} values indicative of thin disks, which is in contrast to minor-to-major axis ratio studies.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2015

A new optical polarization catalog for the Small Magellanic Cloud: The magnetic field structure

We present a new optical polarimetric catalog for the Small Magellanic Cloud (SMC). It contains a total of 7207 stars, located in the northeast (NE) and Wing sections of the SMC and part of the Magellanic Bridge. This new catalog is a significant improvement compared to previous polarimetric catalogs for the SMC. We used it to study the sky-projected interstellar magnetic field structure of the SMC. Three trends were observed for the ordered magnetic field direction at position angles (PAs) of (65° ± 10°), (115° ± 10°), and (150° ± 10°). Our results suggest the existence of an ordered magnetic field aligned with the Magellanic Bridge direction and SMC’s Bar in the NE region, which have PAs roughly at 115.°4 and 45°, respectively. However, the overall magnetic field structure is fairly complex. The trends at 115° and 150° may be correlated with the SMC’s bimodal structure, observed in Cepheids’ distances and HI velocities. We derived a value of B{sub sky}=(0.947±0.079) μG for the ordered sky-projected magnetic field, and δB=(1.465±0.069) μG for the turbulent magnetic field. This estimate of B{sub sky} is significantly larger (by a factor of ∼10) than the line of sight field derived from Faraday rotation observations, suggesting that most of the ordered field component is on the plane of the sky. A turbulent magnetic field stronger than the ordered field agrees with observed estimates for other irregular and spiral galaxies. For the SMC the B{sub sky}/δB ratio is closer to what is observed for our Galaxy than other irregular dwarf galaxies.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

The three-way junction structure of the HIV-1 PBS-segment binds host enzyme important for viral infectivity

HIV-1 reverse transcription initiates at the primer binding site (PBS) in the viral genomic RNA (gRNA). Although the structure of the PBS-segment undergoes substantial rearrangement upon tRNALys3 annealing, the proper folding of the PBS-segment during gRNA packaging is important as it ensures loading of beneficial host factors. DHX9/RNA helicase A (RHA) is recruited to gRNA to enhance the processivity of reverse transcriptase. Because the molecular details of the interactions have yet to be defined, we solved the solution structure of the PBS-segment preferentially bound by RHA. Evidence is provided that PBS-segment adopts a previously undefined adenosine-rich three-way junction structure encompassing the primer activation stem (PAS), tRNA-like element (TLE) and tRNA annealing arm. Disruption of the PBS-segment three-way junction structure diminished reverse transcription products and led to reduced viral infectivity. Because of the existence of the tRNA annealing arm, the TLE and PAS form a bent helical structure that undergoes shape-dependent recognition by RHA double-stranded RNA binding domain 1 (dsRBD1). Mutagenesis and phylogenetic analyses provide evidence for conservation of the PBS-segment three-way junction structure that is preferentially bound by RHA in support of efficient reverse transcription, the hallmark step of HIV-1 replication.

59 BASIC BIOLOGICAL SCIENCES↗