Search NASA⌕ Search

SEARCH · Search NASA

Results for “structural modification”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 865 records · Page 48
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Effective reduction in the nanoparticle sizes of NiO obtained via the pyrolysis of nickel malonate precursor modified using oleylamine surfactant

Nickel oxide nanoparticles were synthesized via thermal decomposition of two precursors, the first, a simple nickel malonate and the second, a nickel malonate modified by oleylamine, a surfactant, both having been synthesized by precipitation. While FTIR, TGA and ToF-SIMS were used to characterize the two precursors and to show the presence of oleylamine in the modified precursor, XRD, SEM, TEM and BET were employed to investigate the structure, the morphology and the specific surface area of the decomposition products obtained after pyrolysis. The results showed that the modification of nickel malonate by oleylamine was effective. The XRD results, which showed a cubic structure for the NiO obtained, suggest with SEM an important particle size reduction (at least 54%) when oleylamine was used to modify the nickel malonate precursor. The SEM images also showed a well-defined spherical nanoparticle morphology in both cases, not affected by the presence of oleylamine. The TEM also confirmed the reduction of particle size and their spherical nature but at the same time showed that, in the presence of oleylamine, there was no agglomeration resulting in a more uniform particle size distribution. The specific surface area of the NiO obtained by the oleylamine-modified precursor was 4.7 times larger than that obtained with the regular precursor. This again confirms the particle size reduction. - Highlights: • Nickel malonate precursor has been synthesized by precipitation method. • This precursor was successfully modified by a surfactant (oleylamine). • NiO was identified as the decomposition products of the previous precursors. • Oleylamine has provoked around 54% of particle size reduction of the NiO.

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

Skeletal stem cell and bone implant interactions are enhanced by LASER titanium modification

Purpose: To evaluate the osteo-regenerative potential of Titanium (Ti) modified by Light Amplification by Stimulated Emission of Radiation (LASER) beam (Yb-YAG) upon culture with human Skeletal Stem Cells (hSSCs{sup 1}). Methods: Human skeletal cell populations were isolated from the bone marrow of haematologically normal patients undergoing primary total hip replacement following appropriate consent. STRO-1{sup +} hSSC{sup 1} function was examined for 10 days across four groups using Ti discs: i) machined Ti surface group in basal media (Mb{sup 2}), ii) machined Ti surface group in osteogenic media (Mo{sup 3}), iii) LASER-modified Ti group in basal media (Lb{sup 4}) and, iv) LASER-modified Ti group in osteogenic media (Lo{sup 5}). Molecular analysis and qRT-PCR as well as functional analysis including biochemistry (DNA, Alkaline Phosphatase (ALP{sup 6}) specific activity), live/dead immunostaining (Cell Tracker Green (CTG{sup 7})/Ethidium Homodimer-1 (EH-1{sup 8})), and fluorescence staining (for vinculin and phalloidin) were undertaken. Inverted, confocal and Scanning Electron Microscopy (SEM) approaches were used to characterise cell adherence, proliferation, and phenotype. Results: Enhanced cell spreading and morphological rearrangement, including focal adhesions were observed following culture of hSSCs{sup 1} on LASER surfaces in both basal and osteogenic conditions. Biochemical analysis demonstrated enhanced ALP{sup 6} specific activity on the hSSCs{sup 1}-seeded on LASER-modified surface in basal culture media. Molecular analysis demonstrated enhanced ALP{sup 6} and osteopontin expression on titanium LASER treated surfaces in basal conditions. SEM, inverted microscopy and confocal laser scanning microscopy confirmed extensive proliferation and migration of human bone marrow stromal cells on all surfaces evaluated. Conclusions: LASER-modified Ti surfaces modify the behaviour of hSSCs.{sup 1} In particular, SSC{sup 1} adhesion, osteogenic gene expression, cell morphology and cytoskeleton structure were affected. The current studies show Ti LASER modification can enhance the osseointegration between Ti and skeletal cells, with important implications for orthopaedic application. - Highlights: • Bone stem cells on LASER Ti surface display enhanced cell growth and viability. • Bone stem cells on LASER Ti surface exhibit marked biocompatibility. • Human bone stem cells on LASER Ti surface exhibit altered morphology. • LASER Ti enhance osteogenic differentiation of human bone skeletal stem cells. • LASER Ti provides a unique approach to enhance osseointegration with the material.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2017

Polymorphism and structure of Nd{sub 2}MоO{sub 6} single crystals

The tetragonal and monoclinic modifications of Nd{sub 2}MoO{sub 6} single crystals have been investigated by X-ray diffraction. The analysis has been on laboratory sources (2D CCD diffractometers: Xcalibur S (Shared Research Center, Institute of Crystallography, Russian Academy of Sciences) and BRUKER Smart APEX 2 (Shared Research Center, Institute of General and Inorganic Chemistry, Russian Academy of Sciences)) and on a synchrotron radiation source (ESRF, Grenoble, PILATUS@SNBL diffractometer). Local displacements of all atoms in the oxymolybdate structure have been revealed for the first time using electron density difference maps. Possible violation of the translational periodicity in the distribution of Mo and Nd atoms over types is indirectly confirmed, and statistical disorder of oxygen atoms is revealed. The results of the study confirm the previous suggestion that polymorphic transformations occur in oxymolybdates at a very low rate and, apparently, continuously in a wide temperature range. With an increase in temperature, layers undergo ordering according to the cation type as a result of the phase transition from the monoclinic to the tetragonal phase.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Influence of bias voltage on structural and optical properties of TiN{sub x} thin films

In the present work, Ti thin films were deposited on Si substrate using DC sputtering technique. Indigenous hot cathode arc discharge plasma system was used for nitriding over these samples, where the plasma parameters and work piece can be controlled independently. A mixture of H{sub 2} and N{sub 2} gases (in the ratio of 80:20) was supplied into the plasma chamber. The effect of bias voltage on the crystal structure, morphology and optical properties was investigated by employing various physical techniques such as X-ray Diffraction, Atomic Force Microscopy and UV-Vis spectrometry. It was found that bias voltage affects largely the crystal structure and band gap which in turn is responsible for the modifications in optical properties of the deposited films.

36 MATERIALS SCIENCE↗
DOE OSTI2022

AMTS update for STTR

Advanced nuclear reactor systems currently in development include designs that utilize higher energy neutron spectrums, higher temperatures, and corrosive environments that are quite different from the current fleet of nuclear power plants in use today. As a result, new structural materials must be developed and qualified for use to support these advanced systems. For example, research is currently being conducted on a new class of materials known as multi-principle-element-alloys. These alloys show some promise to be able to meet the structural needs of these challenging reactor systems. However, due to the vast available compositional space, and the limited amount of research conducted thus far, Idaho National Laboratory (INL)sought a way to advanced mechanical testing capability for highly irradiated structural materials to increase both throughput and higher fidelity data analysis through incorporation of digital image correlation. The Automated Mechanical Testing System accomplishes these tasks by automating the testing and incorporating digital image correlation to provide higher fidelity data. INL has now received this system and is currently performing functional testing and training. INL is also performing some modifications to the system to allow for installation into a remote shielded enclosure where testing of irradiated structural materials can be performed. After testing, training, and modifications of the system are complete, INL will install the system into a shielded enclosure and begin using the system to test irradiated structural materials.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Strain tuning of electronic structure in Bi 4 Ti 3 O 12 -LaCoO 3 epitaxial thin films

In this study, we investigated the crystal and electronic structures of ferroelectric Bi 4 Ti 3 O 12 single-crystalline thin films site-specifically substituted with LaCoO 3 (LCO). The epitaxial films were grown by pulsed laser epitaxy on NdGaO 3 and SrTiO 3 substrates to vary the degree of strain. With increasing the LCO substitution, we observed a systematic increase in the c-axis lattice constant of the Aurivillius phase related with the modification of pseudo-orthorhombic unit cells. These compositional and structural changes resulted in a systematic decrease in the band gap, i.e., the optical transition energy between the oxygen 2p and transition-metal 3d states, based on a spectroscopic ellipsometry study. In particular, the Co 3d state seems to largely overlap with the Ti t 2g state, decreasing the band gap. Interestingly, the applied tensile strain facilitates the band-gap narrowing, demonstrating that epitaxial strain is a useful tool to tune the electronic structure of ferroelectric transition-metal oxides.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Te Vacancy‐Driven Anomalous Transport in ZrTe 5 and HfTe 5

Abstract The strongly sample‐dependent anomalous transport properties observed in the layered Dirac materials ZrTe 5 and HfTe 5 are known to strongly correlate with the presence of Te vacancies. One phenomenon, a negative longitudinal magnetoresistance (NLMR), is widely speculated to be a signature of broken chiral symmetry. However, the role of electronic structure in the sample dependence of the transport properties of these materials is poorly understood. This prompts the question as to whether the NLMR is a genuine signature of the chiral anomaly in ZrTe 5 and HfTe 5 . In this work, the effect of Te vacancies on the electronic structure of ZrTe 5 and HfTe 5 is investigated via first‐principles calculations. Te vacancies serve two purposes: modification of the cell volume via effective compressive strain and production of local changes to the electronic structure. The reorganization of the electronic structure near the Fermi energy indicates that Te vacancies can rationalize conflicting reports in spectroscopic and transport measurements that have remained elusive in prior first‐principles studies. These results show that Te vacancies contribute, in part, to the anomalous transport properties of ZrTe 5 and HfTe 5 but, critically, do not eliminate the possibility of a genuine manifestation of the chiral anomaly in these materials.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Selectivity mechanisms of ion intercalation in Prussian blue analogs

Prussian blue analogs (PBAs) are a family of materials with facile, reversible, and selective ion transport capability for various ions via electrochemical intercalation, owing to their vacancy structure. The large tunable compositional space of PBAs allows for manipulation of intercalation behavior and selectivity by controlling structural vacancy level through choice of transition metal centers and modifications to the synthesis process. However, a lack of understanding of the mechanisms of ion selectivity hinders the material’s design process. Here, for this work, we investigated the origins of ion selectivity using a model PBA, copper hexacyanoferrate, and focused on eight technologically and biologically prominent ions, for which we determined a sequence of selectivity: Rb + > K + > Na + > Ba 2+ > Sr 2+ ≈ Ca 2+ > Mg 2+ > Li + . We provide electrochemical, structural, and redox evidence of strong correlation between the ion identity, the dominant charge-compensating redox, and preferred occupancy site. Specifically, using synchrotron anomalous X-ray diffraction (AXRD), we reveal that monovalent ions exhibit significant association with the corner sites of the unit cell and iron redox, whereas divalent ions display affinity toward the center site with higher ratios of copper redox. Informed by selectivity results, we applied CuHCFe to Li purification and achieved 99.9% purity. Our findings demonstrate an approach to elucidating ion intercalation behavior in order to distinguish and manipulate material properties to optimize separation performance.

Prussian blue analog↗
DOE OSTI2016

Structures of human ADAR2 bound to dsRNA reveal base-flipping mechanism and basis for site selectivity

Adenosine deaminases acting on RNA (ADARs) are editing enzymes that convert adenosine to inosine in duplex RNA, a modification reaction with wide-ranging consequences in RNA function. Understanding of the ADAR reaction mechanism, the origin of editing-site selectivity, and the effect of mutations is limited by the lack of high-resolution structural data for complexes of ADARs bound to substrate RNAs. In this paper, we describe four crystal structures of the human ADAR2 deaminase domain bound to RNA duplexes bearing a mimic of the deamination reaction intermediate. These structures, together with structure-guided mutagenesis and RNA-modification experiments, explain the basis of the ADAR deaminase domain's dsRNA specificity, its base-flipping mechanism, and its nearest-neighbor preferences. In addition, we identified an ADAR2-specific RNA-binding loop near the enzyme active site, thus rationalizing differences in selectivity observed between different ADARs. In conclusion, our results provide a structural framework for understanding the effects of ADAR mutations associated with human disease.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

CASTELO: clustered atom subtypes aided lead optimization—a combined machine learning and molecular modeling method

Background: Drug discovery is a multi-stage process that comprises two costly major steps: pre-clinical research and clinical trials. Among its stages, lead optimization easily consumes more than half of the pre-clinical budget. We propose a combined machine learning and molecular modeling approach that partially automates lead optimization workflow in silico, providing suggestions for modification hot spots. Results: The initial data collection is achieved with physics-based molecular dynamics simulation. Contact matrices are calculated as the preliminary features extracted from the simulations. To take advantage of the temporal information from the simulations, we enhanced contact matrices data with temporal dynamism representation, which are then modeled with unsupervised convolutional variational autoencoder (CVAE). Finally, conventional and CVAE-based clustering methods are compared with metrics to rank the submolecular structures and propose potential candidates for lead optimization. Conclusion: With no need for extensive structure-activity data, our method provides new hints for drug modification hotspots which can be used to improve drug potency and reduce the lead optimization time. It can potentially become a valuable tool for medicinal chemists.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

The structural basis of N -acyl-$α$-amino-β-lactone formation catalyzed by a nonribosomal peptide synthetase

Nonribosomal peptide synthetases produce diverse natural products using a multidomain architecture where the growing peptide, attached to an integrated carrier domain, is delivered to neighboring catalytic domains for bond formation and modification. Investigation of these systems can lead to the discovery of new structures, unusual biosynthetic transformations, and to the engineering of catalysts for generating new products. The antimicrobial β-lactone obafluorin is produced nonribosomally from dihydroxybenzoic acid and a β-hydroxy amino acid that cyclizes into the β-lactone during product release. Here we report the structure of the nonribosomal peptide synthetase ObiF1, highlighting the structure of the β-lactone-producing thioesterase domain and an interaction between the C-terminal MbtH-like domain with an upstream adenylation domain. Biochemical assays examine catalytic promiscuity, provide mechanistic insight, and demonstrate utility for generating obafluorin analogs. These results advance our understanding of the structural cycle of nonribosomal peptide synthetases and provide insights into the production of β-lactone natural products.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

Efficient SnO{sub 2}/CuO/porous silicon nanocomposites structure for NH{sub 3} gas sensing by incorporating CuO nanoparticles

In this paper, a porous silicon (Psi) surface modification process, including the incorporating of pure and CuO mixed SnO{sub 2} within a Psi layer, was investigated. A Psi layer with a pore-like structure prepared via laser-assisted etching process with a laser illumination intensity of (40) mW/cm{sup 2} was employed as a substrate for materialization SnO{sub 2}/CuO/Psi nanocomposites for gas sensing application. Pure SnO{sub 2} and SnO{sub 2}:CuO nanoparticles were synthesized via a chemical spray pyrolysis process on the Psi surface at 350 °C. The materialization of SnO{sub 2}:CuO/Psi nanocomposites were recognized through Field-Emission Scanning Electron Microscopy, X-ray Diffraction, Atomic Force Microscopy, and Energy-dispersive X-ray Analysis. The results displayed that the morphological properties of SnO{sub 2}:CuO nanoparticles were definitely controlled by varying the CuO contents. Different shapes (nearly cubic shape and spherical shape) with various sizes of SnO{sub 2} and SnO{sub 2}:CuO within the Psi surface were achieved by increasing the CuO content. SnO{sub 2}:CuO/Psi nanocomposites, plans, grain size, average surface roughness, homogeneity and specific surface area of SnO{sub 2}:CuO nanoparticles were considerably influenced by CuO content. The lower grain size and higher average surface roughness and specific surface area were attained when the percentage of CuO was about 30% within the structure of 70% SnO{sub 2}:30% CuO, and the performance of the NH{sub 3} gas sensor revealed a short response time with a high sensitivity of (88%).

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2019

Chemical Modifications of Cyclodextrin and Chitosan for Biological and Environmental Applications: Metals and Organic Pollutants Adsorption and Removal

New advances in polymer science and their possible applications have increased in recent years highlighting their important and desired properties. Regarding cyclodextrin and chitosan polymers, they are used in many fields such as agriculture, pharmaceutical, food industry, medicine and in electrochemical sensors. Carefully designed studies are therefore required in order to understand the toxicology, the ways of interaction, biodegradation rate and other parameters of these compounds before using them. This review presents the finding of studies of these polymers applications mainly on drug delivery system and pollutants removal. In addition, modifications are made to enhance their properties and enable some reactions, here it is discussed the most used modification techniques and how they change chitosan and cyclodextrin structure. Although there has been an increase in the number of studies in these areas, further progress is needed to improve understanding of the interaction between the polymers and the compounds of interest, besides their mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Synthesis and characterization of metastable, 20 nm-sized Pna2{sub 1}-LiCoPO{sub 4} nanospheres

The majority of research activities on LiCoPO{sub 4} are focused on the phospho-olivine (space group Pnma), which is a promising high-voltage cathode material for Li-ion batteries. In contrast, comparably little is known about its metastable Pna2{sub 1} modification. Herein, we present a comprehensive study on the structure–property relationships of 15–20 nm Pna2{sub 1}-LiCoPO{sub 4} nanospheres prepared by a simple microwave-assisted solvothermal process. Unlike previous reports, the results indicate that the compound is non-stoichiometric and shows cation-mixing with Co ions on the Li sites, which provides an explanation for the poor electrochemical performance. Co L{sub 2,3}-edge X-ray absorption spectroscopic data confirm the local tetrahedral symmetry of Co{sup 2+}. Comprehensive studies on the thermal stability using thermogravimetric analysis, differential scanning calorimetry, and in situ powder X-ray diffraction show an exothermic phase transition to olivine Pnma-LiCoPO{sub 4} at 527 °C. The influence of the atmosphere and the particle size on the thermal stability is also investigated. - Graphical abstract: Blue nano-sized Pna2{sub 1}-LiCoPO{sub 4,} featuring tetrahedrally-coordinated Co{sup 2+}, was synthesized in a rapid one-step microwave-assisted solvothermal process. The phase relation between this metastable and the stable polymorph was analyzed and electrochemical properties are discussed. - Highlights: • Preparation of uniform 15–20 nm nanospheres of metastable Pna2{sub 1}-LiCoPO{sub 4} polymorph. • Structure redetermination shows cation-mixing (Co blocking Li sites). • In situ investigation of phase transformation to olivine Pnma-LiCoPO{sub 4} at 527 °C. • Pna2{sub 1}-LiCoPO{sub 4} reemerges as a stable high-temperature phase above 800 °C. • X-ray absorption spectroscopy confirms local tetrahedral symmetry (T{sub d} Co{sup 2+}).

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

Hierarchically macro–mesoporous TiO{sub 2} film via self-assembled strategy for enhanced efficiency of dye sensitized solar cells

Highlights: • A new hierarchically macro–mesoporous TiO{sub 2} film is fabricated via TiF{sub 4} hydrolysis. • TiF{sub 4} hydrolysis is accompanied with self-assembled process of TiO{sub 2} nanoparticles. • The hierarchically porous TiO{sub 2} films show higher performance than nonporous film. - Abstract: The hierarchically porous structure of TiO{sub 2} film plays an important role on improved photoelectric conversion efficiency in dye-sensitized solar cells (DSSCs). It is highly required to develop a facile strategy to prepare the hierarchical porous photoelectrode. In this study, a novel hierarchically macro–mesoporous TiO{sub 2} film as photoelectrode of DSSCs is fabricated by a self-assembled process of TiO{sub 2} nanoparticles via TiF{sub 4} hydrolysis. The hydrolysis of TiF{sub 4} is accompanied with self-assembled process of TiO{sub 2} nanoparticles on the surface of electrophoretic-deposited titanate nanotube film which provides effective active sites for the deposition of TiO{sub 2} nanoparticles owing to a large amount of hydroxyl groups, resulting in the formation of hierarchically porous structures. The hierarchically porous TiO{sub 2} film is mainly composed of mesopores with a size of 2–50 nm and macropores with a wide range of 0.5–5 μm, which contribute to an obviously higher conversion performance (6.70%) than nonporous P25-TiO{sub 2} film (4.01%). The main reasons for enhanced conversion efficiency of hierarchically porous TiO{sub 2} film can be attributed to adsorption of more dye molecules, rapid diffusion and efficient transport of electrolyte, and longer electron lifetime. This work may provide new insights into preparing porous structure of TiO{sub 2} films in DSSCs for modification of photoelectric conversion efficiency.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Polymer microfilters with nanostructured surfaces for the culture of circulating cancer cells

There is a critical need to improve the accuracy of drug screening and testing through the development of in vitro culture systems that more effectively mimic the in vivo environment. Surface topographical features on the nanoscale level, in short nanotopography, effect the cell growth patterns, and hence affect cell function in culture. We report the preliminary results on the fabrication, and subsequent cellular growth, of nanoscale surface topography on polymer microfilters using cell lines as a precursor to circulating tumor cells (CTCs). To create various nanoscale features on the microfilter surface, we used reactive ion etching (RIE) with and without an etching mask. An anodized aluminum oxide (AAO) membrane fabricated directly on the polymer surface served as an etching mask. Polymer filters with a variety of modified surfaces were used to compare the effects on the culture of cancer cell lines in blank culture wells, with untreated microfilters or with RIE-treated microfilters. We then report the differences of cell shape, phenotype and growth patterns of bladder and glioblastoma cancer cell lines after isolation on the various types of material modifications. Our data suggest that RIE modified polymer filters can isolate model cell lines while retaining ell viability, and that the RIE filter modification allows T24 monolayering cells to proliferate as a structured cluster. Copyright 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Makarova, Olga V.↗