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ADAR activation by inducing a syn conformation at guanosine adjacent to an editing site

Abstract ADARs (adenosine deaminases acting on RNA) can be directed to sites in the transcriptome by complementary guide strands allowing for the correction of disease-causing mutations at the RNA level. However, ADARs show bias against editing adenosines with a guanosine 5′ nearest neighbor (5′-GA sites), limiting the scope of this approach. Earlier studies suggested this effect arises from a clash in the RNA minor groove involving the 2-amino group of the guanosine adjacent to an editing site. Here we show that nucleosides capable of pairing with guanosine in a syn conformation enhance editing for 5′-GA sites. We describe the crystal structure of a fragment of human ADAR2 bound to RNA bearing a G:G pair adjacent to an editing site. The two guanosines form a Gsyn:Ganti pair solving the steric problem by flipping the 2-amino group of the guanosine adjacent to the editing site into the major groove. Also, duplexes with 2′-deoxyadenosine and 3-deaza-2′-deoxyadenosine displayed increased editing efficiency, suggesting the formation of a Gsyn:AH+anti pair. This was supported by X-ray crystallography of an ADAR complex with RNA bearing a G:3-deaza dA pair. This study shows how non-Watson–Crick pairing in duplex RNA can facilitate ADAR editing enabling the design of next generation guide strands for therapeutic RNA editing.

Doherty, Erin E.↗

Apollo 17 1-2 mm fines - Mineralogy and petrology

Nine 1-2 mm Apollo 17 soil samples from the South Massif and the Sculptured Hills are examined using petrographic and microprobe techniques. Each soil was separated into six groupings based on macroscopic features observed under a stereomicroscope. The groups and their characteristics are described. Minor differences observed include a higher content of fine-grained, dark, friable breccia and a higher content of high-Mg mafic-bearing fragments in the Sculptured Hills soils. The olivine and pyroxene compositions for light breccia from the soil samples are summarized. During the soil examination, several distinctive fragments seen include coarse orthopyroxene-plagioclase fragments with diopside-rich veins, a plagioclase-forsterite fragment with an igneous texture and a pyroxene-plagioclase fragment with isotropic, subhedral plagioclase grains.

Steele, I. M.↗

Carbonate deposition during the late Proterozoic Era: an example from Spitsbergen

Carbonate sediments reflect the physico-chemical and biological circumstances of their formation; thus, features of limestones and dolomites may provide insights into both environmental and evolutionary change through geological time. The Upper Proterozoic (approx 800-700 Ma) Akademikerbreen Group, Spitsbergen, comprises 2000 m of carbonates, with only minor intercalations of quartz arenite and shale. Although Proterozoic carbonates are often seen as predominantly dolomitic, the Akademikerbreen Group is about 45 percent limestone. Stromatolites are conspicuous in outcrop but constitute only 25 percent of the total section. Micrites and coarser intraclastic carbonates derived mainly from micritric precursors comprise 60 percent of the group, while oolites make up the remaining 15 percent. Distinctive sedimentary features of the group include giant (up to 16 mm) ooids, very early diagenetic calcite nodules and cements, micrites containing subaqueous shrinkage cracks filled with equant microspar cement, and strong 13C enrichment in both carbonates and co-occurring organic matter. The principal features of Akademikerbreen carbonates are widely distributed in coeval successions. However, these rocks appear to differ from older limestones and dolomites in their relative abundance of grainstones and, perhaps, micrites, as well as their paucity of tufa-like laminates and columnar or coniform stromatolites that preserve petrographic evidence of in situ precipitation as a dominant means of carbonate accretion. Upper Proterozoic carbonates also differ from Paleozoic accumulations, but the transition is not abrupt. Most changes accompanying the Proterozoic/Phanerozoic transition can be interpreted in terms of the consequences rather than the causes of metazoan and metaphyte evolution, including the evolution of biomineralization. Carbonate sedimentology reinforces data from other sources which indicate the last 200 to 300 Ma of the Proterozoic Eon was a distinctive interval of Earth history.

NASA Discipline Number 52-30↗

Pink Spinel in Apollo Impact Melt Rock 68815: Implications for Mg-Suite Magmatism

Introduction: Magnesian rocks from the lunar highlands are collectively termed the Mg-suite. Characterized by high (>60) Mg# (molar 100×Mg/[Mg+Fe]) in mafic phases and calcic plagioclase, these rocks are plutonic to hypabyssal in origin, and include a range of bulk mineralogies such as troctolites, dunites, norites, gabbronorites, and spinel troctolites [1]. These Mg-suite lithologies have distinct trace element concentrations and ratios that differentiate them from other lunar rock types. These rocks are ancient, generally dated to between 4.5 and 4.1 Ga, although it is unknown if this represents the full range of Mg-suite ages [1–2]. Among the Mg-suite lithologies, the spinel troctolites are relatively rare, to date only found in polymict breccias [3]. Spinel troctolites, as their name suggests, consist of calcic plagioclase and forsteritic olivine, with minor amounts of spinel (MgAl2O4), ± pyroxene and cordierite [1,4]. This form of spinel is often called ‘pink’ spinel because of its appearance in thin section under plane polarized light (PPL; Fig. 1), due to minor amounts of Cr. Spinel troctolites are generally plutonic or hypabyssal in origin (subsequently exhumed and incorporated into polymict breccias), or formed through impact processes (e.g., crystalline impact melt) [5]. A spinel-rich lithology has also been found in the Moscoviense region of the Moon via the Moon Mineralogy Mapper (M3) and lacks other mafic phases [6]. Finally, while the Mg-suite sampled thus far consists of plutonic (or hypabyssal) rocks, the question remains if such magmas could have erupted on the surface of the Moon [7]. These magmas have much lower density than mare basalts, but little sample or remote sensing evidence has been found to support the idea that extrusive Mg-suite volcanism occurred [7]. Here, we present a coordinated microanalytical study of spinel-bearing lithic and mineral clasts found in Apollo sample 68815. These data will be used to understand their petrogenesis (magmatic or impact) and modification histories, and to shed light on the existence of volcanic Mg-suite rocks. Sample Description: Apollo sample 68815 is a polymict impact melt breccia containing a variety of lithic and mineral fragments embedded in devitrified impact melt. This sample was chipped off the top of a boulder at Station 8 during the Apollo 16 mission and had an original weight of nearly 1.8 kg. In this study, we investigated two polished thin sections of 68815: 68815,17 and 68815,148, both containing spinel. Methods: The thin sections of 68815 were studied using optical light microscopy (PPL, cross-polarized light, and reflected light) with a Keyence VHX-7100 Digital Microscope. Each section was then X-ray mapped for 13–14 elements using a Cameca SX100 electron probe microanalyzer (EPMA) located in the Kuiper Materials Imaging and Characterization Facility (KMICF) at the University of Arizona. We have obtained geochemical information about the phases (olivine, plagioclase, spinel, pyroxene) in the thin sections also using the EPMA. In addition, we have used ThermoScientific Helios NanoLab 660 Focused-Ion-Beam Scanning-Electron Microscope (FIB-SEM) and a Hitachi S-4800 SEM (both in KMICF) to obtain backscattered electron (BSE) images and energy dispersive Xray spectrometry (EDS) maps of areas of interest. Using a JEOL 7900F SEM at the Astromaterials Research & Exploration Science (ARES) at NASA Johnson Space Center (JSC), we have obtained electron backscatter diffraction (EBSD) maps of the spinel-bearing portions of the thin sections. The EBSD data were collected under beam conditions of 20 kV, and ~90 μA, with step sizes varying from 0.05 to 2 μm. Following EBSD data collection, we processed the data using AZtecCrystal and MTEX, a free MATLAB toolbox. Results: We have found clasts with subophitic textures, that consist of primarily olivine and plagioclase, with minor amounts of pink Mg-Al spinel and pyroxene (Fig. 1). These clasts are up to ~1 mm in length and contain spinels up to 50 μm across. We have additionally identified pink Mg-Al spinels within the impact melt (i.e., not contained in lithic clasts) in both thin sections. In one instance, a single spinel grain is approximately 300 μm across (Fig. 1b, 2). The spinel fragments embedded in impact melt have varying compositions, typically distinct from the compositions of spinels in the lithic clasts. Spinel-Bearing Clasts: Ten lithic clasts with similar textures and mineral compositions were identified between 68815,17 (two clasts) and ,148 (eight clasts). These clasts fall into two groups. The first has skeletal olivine with intergranular plagioclase, with minor amounts of pyroxene and spinel (Fig. 1a, 2c, 2d). The spinel in these clasts are found amid the plagioclase. The second group have an intergranular texture of olivine and plagioclase, again with minor spinel and pyroxene. The second group may contain spinels surrounded by plagioclase, and spinels enclosed in olivine. Spinels located within both clast types range from no apparent Cr zoning, to reverse zoning (Cr-enrichment inward; Fig. 2d), to normal zoning (Cr-enrichment outward). In the clasts thus far investigated with EPMA, plagioclase compositions range from An# (molar 100×Ca/[Ca+Na+K]) 92–96. Olivine Mg# ranged from 77 to 94, while pyroxene had Mg# from 54–84. Spinel in the clasts have Cr# (molar 100×Cr/[Cr+Al]) 2–4 and Mg# 88–91, which is within the range of pristine and plutonic spinel troctolites [8]. Isolated Spinels: These crystals are generally euhedral to subhedral, and can exhibit reverse Cr zoning (Cr enrichment inward) or no apparent Cr zoning. The spinels thus far investigated via EPMA have Cr# 9–14 and Mg# 65–82. The Cr# for these spinels is within the range reported by [8], but have lower Mg#. Future Work: We will continue to process the EBSD data for these lithic and mineral clasts. We will also continue to characterize these clasts using EPMA and SEM. By thoroughly characterizing the various spinels and spinel-bearing clasts, we aim to constrain the petrogenesis of these minerals and rock fragments. Acknowledgments: We thank NASA for the loan of these thin sections. We thank Ken Domanik and Jerry Chang for their support with data collection. Work was supported by a University of Arizona RII Core Facilities Pilot Program grant and start-up funds to JJB. We acknowledge support from NASA’s Planetary Science Research program for analysis performed at JSC. References: [1] Shearer C. K. et al. (2015) Am. Min. 100, 294–325. [2] Borg L. E. et al. (2020) GCA 290, 312–332. [3] Warren P. H. (1993) Am. Min. 78, 360–376. [4] Dymek R. F. et al. (1976) LPS VII, 2335–2378. [5] Treiman et al. (2019) Am. Min. 104, 370–384. [6] Pieters et al. (2011) JGR: Plan. 116:E00G08. [7] Prissel et al. (2016) Icarus 277, 319–329. [8] Prissel et al. (2016) Am. Min. 101, 1624–1635.

spinel↗

The role of histone tails in the nucleosome: A computational study

Histone tails play an important role in gene transcription and expression. We present here a systematic computational study of the role of histone tails in the nucleosome, using replica exchange molecular dynamics simulations with an implicit solvent model and different well-established force fields. We performed simulations for all four histone tails, H4, H3, H2A, and H2B, isolated and with inclusion of the nucleosome. The results confirm predictions of previous theoretical studies for the secondary structure of the isolated tails but show a strong dependence on the force field used. In the presence of the entire nucleosome for all force fields, the secondary structure of the histone tails is destabilized. Specific contacts are found between charged lysine and arginine residues and DNA phosphate groups and other binding sites in the minor and major DNA grooves. Using cluster analysis, we found a single dominant configuration of binding to DNA for the H4 and H2A histone tails, whereas H3 and H2B show multiple binding configurations with an equal probability. The leading stabilizing contribution for those binding configurations is the attractive interaction between the positively charged lysine and arginine residues and the negatively charged phosphate groups, and thus the resulting charge neutralization. Lastly, we present results of molecular dynamics simulations in explicit solvent to confirm our conclusions. Results from both implicit and explicit solvent models show that large portions of the histone tails are not bound to DNA, supporting the complex role of these tails in gene transcription and expression and making them possible candidates for binding sites of transcription factors, enzymes, and other proteins.

59 BASIC BIOLOGICAL SCIENCES↗

Improving the Success of Underrepresented Populations in Computer and Computational Science Research with the CRA-W Women and URMD Grad Cohort Workshops

The Computing Research Association’s Committee on Widening Participation (CRA-WP) aims to increase the number of individual researchers from underrepresented groups in computing (UGC) (including women, underrepresented minorities, and persons with disabilities) who participate and succeed in computer science research at every stage of the research pipeline. Achieving these objectives requires that an increasing number of individuals from UGC start and progress to the next stage. The CRA-WP Grad Cohort Workshops are focused at the graduate level to maximize the likelihood participants will successfully complete their graduate degrees. Factors such as role models, skills, competence, confidence, mentoring, social support, and development of identity as a researcher help students to persist in graduate school, while factors such as sexism, racism, and dissatisfaction with their graduate program may cause them to leave. We, therefore, help first, second, and third year students build their skills, research strategies, and confidence; meet potential mentors from outside their institutions; develop connections with each other and with their research communities; and inform them about strategies for successful publishing, speaking, and advisor management strategies. By targeting early graduate students, we seek to help them stay in graduate school and in research.

96 KNOWLEDGE MANAGEMENT AND PRESERVATION↗

Outcomes After Transarterial Embolization of Neuroendocrine Tumor Liver Metastases Using Spherical Particles of Different Sizes

Purpose: To evaluate initial response and overall survival of neuroendocrine tumor (NET) liver metastases initially treated with transarterial embolization (TAE) using spherical particles of different sizes. Methods: A single-institution retrospective review was performed of 160 patients with NET liver metastases initially treated with TAE using < 100 µm (n = 77) or only ≥ 100 µm (n = 83) spherical particles. For each patient, we evaluated: initial response by mRECIST, time to progression, overall survival, complications, primary site, tumor grade and degree of differentiation, volume of liver disease, extrahepatic disease, NET-related symptoms, comorbidities, Child–Pugh score, performance status, lobar versus selective embolization, and arteriovenous shunting. Results: Initial response was higher for TAE using particles < 100 versus TAE using only particles ≥ 100 μm (64 vs 42%, p = 0.007). Multivariate logistic regression showed that use of particles < 100 μm and liver < 50% replaced with tumor were independent predictors of a better initial response rate. There was no difference in major or minor complications between the two particle size groups. Median overall survival after TAE was 55 months for well- to moderately differentiated NET and 13 months for poorly differentiated or undifferentiated NET. There was no significant difference in survival between TAE patients treated with < 100 versus only ≥ 100-μm particles. Conclusion: NET patients treated with TAE using particles < 100 μm had better initial response, but the same overall survival, compared to TAE using only particles ≥ 100 μm.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

High performance polymers and polymer matrix composites for spacecraft structural applications

A program implemented by NASA Langley Research Center to develop and evaluate new polymers and polymer matrix composites for spacecraft structural applications is examined. Various polymeric films, moldings, and adhesives are evaluated for resistance to atomic oxygen and high energy electron and UV radiation. Thin films from the poly(arylene ether)s containing phenylphosphine oxide groups and the siloxane-epoxies exhibited minor weight loss compared to Kapton polyimide after exposure. Large doses (greater than 10 exp 9 rads) of electron radiation, simulating 30 yr of exposure in GEO, are found to alter the chemical structure of epoxies by both chain scission and cross-linking. The thermal cycling representative of both LEO and GEO environments can cause microcracking in composites which can in turn affect the dimensional stability and produce mechanical property reductions. The processing and fabrication issues associated with precision composite spacecraft components are also addressed.

Bowles, D. E.↗

Comparison of Synthetic and Natural Nakhlite Pyroxenes: Complexity of Minor Elements

Zoning in pyroxenes in martian meteorites contains a rich record of the petrogenesis of these samples. In the clinopyroxene cumulate nakhlite group, major element zoning is generally limited to the outer rims of the pyroxenes. However, minor element zoning, especially of Al, Ti, and Cr, is extensive, complex, and difficult to interpret [e.g., 1-3]. To help mine the rich information about petrogenetic processes from these samples, we have been comparing minor element zoning in synthetic pyroxenes grown under known conditions with zoning observed in natural nakhlite pyroxenes. We have focused on two nakhlites, MIL03346 (MIL), which is one of the most rapidly cooled nakhlites, and Y000593 (Y593), which cooled at a more moderate rate [e.g., 4].

McKay, G.↗

The 1995 NASA guide to graduate support

The future of the United States is in the classrooms of America and tomorrow's scientific and technological capabilities are derived from today's investments in research. In 1980, NASA initiated the Graduate Student Researchers Program (GSRP) to cultivate additional research ties to the academic community and to support promising students pursuing advanced degrees in science and engineering. Since then, approximately 1300 students have completed the program's requirements. In 1987, the program was expanded to include the Underrepresented Minority and Disabled Focus (UMDF) Component. This program was designed to increase participation of underrepresented groups in graduate study and research and, ultimately, in space science and aerospace technology careers. Approximately 270 minority students have completed the program's requirements while making significant contributions to the nation's aerospace efforts. Continuing to expand fellowship opportunities, NASA announced the Graduate Student Fellowships in Global Change Research in 1990. Designed to support the rapid growth in the study of earth as a system, more than 250 fellowships have been awarded. And, in 1992, NASA announced opportunities in the multiagency High Performance Computing and Communications (HPCC) Program designed to accelerate the development and application of massively parallel processing. Approximately five new fellowships will be awarded yearly. This booklet will guide you in your efforts to participate in programs for graduate student support.

Source record↗

Novel Technique for Hepatic Fiducial Marker Placement for Stereotactic Body Radiation Therapy

Purpose: To report experience with fiducial marker insertion and describe an advantageous, novel technique for fiducial placement in the liver for stereotactic body radiation therapy with respiratory tracking. Methods and Materials: We implanted 1444 fiducials (single: 834; linked: 610) in 328 patients with 424 hepatic lesions. Two methods of implantation were compared: the standard method (631 single fiducials) performed on 153 patients from May 2007 to May 2010, and the cube method (813 fiducials: 610 linked/203 single) applied to 175 patients from April 2010 to March 2013. The standard method involved implanting a single marker at a time. The novel technique entailed implanting 2 pairs of linked markers when possible in a way to occupy the perpendicular edges of a cube containing the tumor inside. Results: Mean duration of the cube method was shorter than the standard method (46 vs 61 minutes; P<.0001). Median numbers of skin and subcapsular entries were significantly smaller with the cube method (2 vs 4, P<.0001, and 2 vs 4, P<.0001, respectively). The rate of overall complications (total, major, and minor) was significantly lower in the cube method group compared with the standard method group (5.7% vs 13.7%; P=.013). Major complications occurred while using single markers only. The success rate was 98.9% for the cube method and 99.3% for the standard method. Conclusions: We propose a new technique of hepatic fiducial implantation that makes use of linked fiducials and involves fewer skin entries and shorter time of implantation. The technique is less complication-prone and is migration-resistant.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Solar cosmic ray micro-events

To study small discrete solar particle events, it has proven useful to define a special class such that the proton flux at energies greater than 20 MeV exceed 0.0001 protons/sq cm-sec-sr-MeV. These increases are termed microevents. An arbitrary upper limit is placed at 2 X 0.02 protons/sq cm-sec-sr-MeV. By demanding a measurable flux above 20 MeV, a better separation from corotating events is achieved and onset times can in general be determined more precisely. Over an observing period extending from May 1967 through December 1971, approximately 105 events were observed. There are several different sources of these small events. Some are produced by moderate to large solar flares near the east limb or by solar flares on the nonvisible disk of the sun. Others are produced by generally minor solar activity: typically in 1N flare, a group of type 3 radio bursts and a well defined X-ray burst. A significant number of this latter type are accompanied by type 2 radio emission. A small sample of the micro-events can be classified as scatter-free events. For these the distance traveled by the particles before their initial detection at earth is on the order of 1.5 AU and observed rise and decay times are much less than normal. Examples of these general types of micro-events and their solar association are discussed.

Mcdonald, F. B.↗

A Role for Adjuvant RFA in Managing Hepatic Metastases from Gastrointestinal Stromal Tumors (GIST) After Treatment with Targeted Systemic Therapy Using Kinase Inhibitors

Purpose: This study was designed to assess the role of radiofrequency ablation (RFA) in the multimodality management of gastrointestinal stromal tumors (GIST) in patients undergoing targeted tyrosine kinase inhibitor therapy (TKI) for liver metastases. Methods: Outcomes of 17 patients who underwent liver RFA for 27 metastatic GIST after TKI therapy, from January 2004 to March 2012, were retrospectively analyzed. Mean maximum tumor diameter was 2.5 ± 1 cm (range 0.9–4.5 cm). In seven patients (group A), RFA of all residual tumors was performed, with curative intent, and TKI therapy was discontinued. In five patients (group B), RFA of all residual tumors was performed upon achieving the best morphological response with TKI therapy, which was maintained after RFA. In another five patients (group C), RFA was performed on individual liver metastases which were progressive under TKI therapy. Results: All 27 targeted tumors were completely ablated, without local recurrence during the mean follow-up period of 49 months. No major complications occurred. Two minor complications were reported (11 %). Only two patients (both in group C) died at 20 and 48 months. Two-year progression-free survival (PFS) after RFA was 29 % in group A, 75 % in group B, and 20 % in group C. Conclusions: RFA in patients, previously treated with TKI, is feasible and safe. Our data suggest that RFA is a useful therapeutic option in patients with metastatic GIST and should be performed at the time of best clinical response with patient maintained under TKI after the procedure.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Potentiation of Hormonal Responses to Hemorrhage and Fasting, but not Hypoglycemia in Conscious Adrenalectomized Rats

Bilateral adrenalectomy (ADRX) in rats removes the source of two major stress-responsive hormones, corticosterone and epinephrine. To test how ADRX rats with-stand stress, we performed the following experiments in adult male rats provided with indwelling femoral arterial and venous cannulae and either ADRX or sham-adrenalectomized (Sham) 3 days later and given 0.5% NaCl to drink. Five to 6 days after adrenal surgery the rats were studied after either a 15 ml/kg.5 min hemorrhage or after an overnight fast followed by insulin-induced hypoglycemia. In fed unstressed ADRX rats, basal mean arterial blood pressure was slightly decreased; heart rate was increased; blood volume, vasopressin, and oxytocin concentrations were not different from sham values; and renin and norepinephrine were significantly elevated. The recovery of arterial pressure after hemorrhage in the ADRX rats was similar to that in the sham group over a 5-h period; however, the responses of vasopressin and oxytocin were significantly greater, and those of renin and norepinephrine were markedly potentiated in the ADRX group. Heart rate recovered faster in the ADRX group and was elevated, compared to the sham value, for most of the 5-h period. Restitution of blood volume was attenuated in the ADRX group, although the restitution of plasma protein was not different between the groups. A significant difference in the change in plasma osmolality between groups after hemorrhage may account for the attenuated restitution of blood volume. After an overnight fast, which reduced blood volume in both groups of rats, the plasma renin concentration rose still further in ADRX rats; the differences in other measured variables observed between fed ADRX and sham groups remained the same. The insulin-induced 50% decrease in glucose caused minor effects on arterial blood pressure and heart rate and occasioned responses in renin and norepinephrine of similar magnitudes in the two groups. We conclude that in the absence of the adrenals, rats restore arterial pressure after hemorrhage remarkably well through potentiation of the responses of other vasoactive neural and hormonal systems. In these studies the marked potentiation of the renin response suggests that the renin-angiotensin system may be important in the maintenance of arterial blood pressure after reductions in blood volume.

Darlington, Daniel N.↗

Petrogenesis of Apollo 12 mare basalts. Part 2: An open system model to explain the pigeonite basalt compositions

Original petrogenetic models suggested that the pigeonite basalts were the evolved equivalents of the olivine basalts. Rhodes et al. concluded that the olivine and pigeonite basalts were co-magmatic, but Neal et al. have demonstrated that these two basaltic groups are distinct and unrelated. The pigeonite suite is comprised of porphyritic basalts with a fine-grained ground mass and range continuously to coarse-grained microgabbros with ophitic to graphic textures. Although it was generally recognized that the pigeonite basalts were derived from the olivine basalts by olivine + minor Cr-spinel fractionation, the compositional gap between these groups is difficult to reconcile with such a model. Indeed, Baldridge et al. concluded that these two basaltic groups could not have been co-magmatic. In this paper, we suggest an open system AFC model for pigeonite basalt petrogenesis. The assimilant is lunar anorthositic crust and the r value used is 0.6. While the choice of assimilant composition is difficult to constrain, the modeling demonstrates the feasibility of this model.

Neal, Clive R.↗

Research and Technology Report: 1997

This volume highlights the most significant results from research and development projects sponsored through NASA's Office of Equal Opportunity Programs, Minority University Research and Education Division, in collaboration with Headquarters Program Offices, during Academic Year 1996-97 and Summer 1996. It includes the work of major multidisciplinary research groups, such as those sponsored under NASA's University Research Centers at Minority Institutions and Institutional Research Awards programs, as well as that of individual principal investigators sponsored under the Faculty Awards for Research or other MUREP programs. It encompasses contributions from 863 students and 388 faculty-level researchers at institutions eligible to compete for MUREP funding, including: Historically Black Colleges and Universities (HBCU), Hispanic-Serving Institutions (HSI), Tribal Colleges and Universities (TCU), and accredited minority colleges or universities with a 50 percent or greater underrepresented minority student enrollment. It stands as a testimony to NASA's response to Executive Orders 12876, 12900, and 13021, which mandate increased Federal support to these classes of institutions. We firmly believe that maintaining America's leadership in aerospace and related areas depends on fully utilizing the talents available at the Nation's minority universities.

Sakimoto, Philip↗

Understanding Methanol Synthesis on Inverse ZnO/CuO x /Cu Catalysts: Stability of CH 3 O Species and Dynamic Nature of the Surface

Inverse ZnO/Cu catalysts are key systems in the conversion of CO 2 , a common atmospheric pollutant, into methanol, a high-value chemical and fuel. The chemistry of methanol and methoxy groups over inverse ZnO/Cu 2 O/Cu(111) catalysts was investigated employing Ambient Pressure X-ray Photoelectron Spectroscopy (AP-XPS), Scanning Tunneling Microscopy (STM) and calculations based on Density Functional Theory (DFT). The results of AP-XPS show that the adsorption of methanol on the binary oxide substrate at 300 K leads to formation of *CH 3 O and *HCOO species with a minor amount of *CH x . Furthermore, most of the methoxy groups disappeared from the surface after heating to 450 K, the onset temperature for the formation of methanol during the hydrogenation of CO 2 . The results of AP-XPS, STM and DFT point to preferential adsorption of methoxy on the ZnO regions of the binary oxide. On the supported ZnO or on a ZnO-Cu 2 O interface, the breaking of the O-H bond in methanol is an exothermic process with a negligible (1-2 kcal/mol) or non-existent energy barrier depending on the size and shape of the ZnO islands. STM

36 MATERIALS SCIENCE↗

Cesium vacancy ordering in phase-separated C s x F e 2 - y S e 2

By simultaneously displaying magnetism and superconductivity in a single phase, the iron-based superconductors provide a model system for the study of magnetism's role in superconductivity. The class of intercalated iron selenide superconductors is unique among these in having the additional property of phase separation and coexistence of two distinct phases—one majority phase with iron vacancy ordering and strong antiferromagnetism, and the other a poorly understood minority microscopic phase with a contested structure. Adding to the intrigue, the majority phase has never been found to show superconductivity on its own while the minority phase has never been successfully synthesized separate from the majority phase. In order to better understand this minority phase, a series of high-quality Cs x Fe 2–y Se 2 single crystals with (0.8 ≤ x ≤ 1;0 ≤ y ≤ 0.3) were grown and studied. Neutron and x-ray powder diffraction performed on ground crystals show that the average I4/mmm structure of the minority phase is distinctly different from the high-temperature I4/mmm parent structure. Moreover, single-crystal diffraction reveals the presence of discrete superlattice reflections that remove the degeneracy of the Cs sites in both the majority and minority phases and reduce their structural symmetries from body centered to primitive. Group theoretical analysis in conjunction with structural modeling shows that the observed superlattice reflections originate from three-dimensional Cs vacancy ordering. This model predicts a 25% vacancy of the Cs site in the minority phase which is consistent with the site's refined occupancy. Magnetization measurements performed in tandem with neutron single-crystal diffraction provide evidence that the minority phase is the host of superconductivity. Lastly, our results also reveal a superconducting dome in which the superconducting transition temperature varies as a function of the nominal valence of iron.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗