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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 145 records · Page 8

Femtosecond Laser Desorption Postionization MS vs ToF-SIMS Imaging for Uncovering Biomarkers Buried in Geological Samples

The study of lipid molecular fossils by traditional biomarker analysis requires bulk sample crushing, followed by solvent extraction, and then the analysis of the extract by gas chromatography-mass spectrometry (GC–MS). This traditional analysis mixes all organic compounds in the sample regardless of their origins, with a loss of information on the spatial distribution of organic molecules within the sample. These shortcomings can be overcome using the chemical mapping of intact samples. Spectroscopic techniques such as UV fluorescence or Raman spectroscopy, laser ablation inductively coupled plasma mass spectrometry, and time-of-flight secondary ion mass spectrometry (ToF-SIMS) are among those elemental and molecular mapping techniques. This study employed femtosecond (fs) laser ablation combined with single-photon ionization, a method called fs-laser desorption postionization mass spectrometry (fs-LDPI-MS). In this work, a pulsed ~75 fs, 800 nm laser was used to ablate the geological sample, which was then photoionized after a few microseconds by a pulsed 7.9 eV vacuum ultraviolet laser. An organic carbon-rich geological sample was used for this study to map hydrocarbon biomarkers in sediments that were previously studied by GC–MS. The petrography of this sample was examined by optical and fluorescence microscopy. It is demonstrated here that fs-LDPI-MS combined with petrography for multimodal imaging can expose buried compounds within the sample via in situ layer removal. When used in conjunction with traditional organic geochemical analysis, this method has the potential to determine the spatial distribution of organic biomarkers in geological material. Finally, fs-LDPI-MS imaging data are compared with ToF-SIMS imaging that is commonly used for such studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Flow-Tagging Velocimetry for Hypersonic Flows Using Fluorescence of Nitric Oxide

We demonstrate a new variation of molecular-tagging velocimetry for hypersonic flows based on laser-induced fluorescence. A thin line of nitric-oxide molecules is excited with a laser beam and then, after a time delay, a fluorescence image of the displaced line is acquired. One component of velocity is determined from the time of flight. This method is applied to measure the velocity profile in a Mach 8.5 laminar, hypersonic boundary layer in the Australian National University s T2 free-piston shock tunnel. The single-shot velocity measurement uncertainty in the freestream was found to be 3.5%, based on 90% confidence. The method is also demonstrated in the separated flow region forward of a blunt fin attached to a flat plate in a Mach 7.4 flow produced by the Australian National University s T3 free-piston shock tunnel. The measurement uncertainty in the blunt fin experiment is approximately 30%, owing mainly to low fluorescence intensities, which could be improved significantly in future experiments. This velocimetry method is applicable to very high-speed flows that have low collisional quenching of the fluorescing species. It is particularly convenient in facilities where planar laser-induced fluorescence is already being performed.

Danehy, Paul M.↗

Viewing Optical Processes at the Nanoscale: Combining Scanning Tunneling Microscopy and Optical Spectroscopy

The combination of optical spectroscopy and scanning tunneling microscopy techniques has the potential to yield the unambiguous single-molecule level insight required to fully understand the complex structure–property relationship of emerging material systems. In this Perspective, we highlight the recent progress of single-molecule absorption detected by scanning tunneling microscopy (SMA-STM) to investigate light–matter interactions of supported (nano)particles, quantum dots, and molecular and thin films at the nanoscale. We further show how the SMA-STM technique has been recently extended to expand the classes of materials that can be investigated as well as recent design modifications that enable both time-resolved imaging and tomography. Finally, we hypothesize how these modifications can be further leveraged to advance our current knowledge of light–matter interactions and how the resulting nanoscale insight can be implemented for future material applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Observation of electron orbital signatures of single atoms within metal-phthalocyanines using atomic force microscopy

Resolving the electronic structure of a single atom within a molecule is of fundamental importance for understanding and predicting chemical and physical properties of functional molecules such as molecular catalysts. However, the observation of the orbital signature of an individual atom is challenging. We report here the direct identification of two adjacent transition-metal atoms, Fe and Co, within phthalocyanine molecules using high-resolution noncontact atomic force microscopy (HR-AFM). HR-AFM imaging reveals that the Co atom is brighter and presents four distinct lobes on the horizontal plane whereas the Fe atom displays a “square” morphology. Pico-force spectroscopy measurements show a larger repulsion force of about 5 pN on the tip exerted by Co in comparison to Fe. Our combined experimental and theoretical results demonstrate that both the distinguishable features in AFM images and the variation in the measured forces arise from Co’s higher electron orbital occupation above the molecular plane. The ability to directly observe orbital signatures using HR-AFM should provide a promising approach to characterizing the electronic structure of an individual atom in a molecular species and to understand mechanisms of certain chemical reactions.

36 MATERIALS SCIENCE↗

The Star-Grazing Bodies in the HD 172555 System

Kiefer et al. reported the detection of in falling Ca(sub II) absorption in HD 172555, a member of the β Pictoris Moving Group (βPMG). We obtained HST Space Telescope Imaging Spectrograph and Cosmic Origins Spectrograph spectroscopy of this star at 2 epochs separated by a week, and we report the discovery of infalling gas in resonant transitions of Si(sub III and IV), C(sub II and IV), and neutral atomic oxygen. Variable absorption is seen in the C(sub II) transitions and is optically thick, with covering factors which range between 58% and 68%, similar to features seen in β Pictoris. The O(sub I) spectral profile resembles that of C(sub II), showing a strong low-velocity absorption to +50 km s(exp −1) in the single spectral segment obtained during orbital night, as well as what may be higher-velocity absorption. Studies of the mid-IR spectrum of this system have suggested the presence of silica. The O(sub I) absorption differs from that seen in Si(sub III), suggesting that the neutral atomic oxygen does not originate in SiO dissociation products but in a more volatile parent molecule such as CO.

HST Space Telescope Imaging Spectrograph↗

Single vs double atom catalyst for N 2 activation in nitrogen reduction reaction: A DFT perspective

Abstract Ammonia synthesis through electrochemical reduction of nitrogen molecules is a promising strategy to significantly reduce the energy consumption in traditional industrial process. Detailed mechanism study of multistep complex nitrogen reduction reaction is prerequisite for the design of highly efficient catalyst. Stable atomically dispersed catalyst with unique geometric and electronic structure is suitable for the mechanism clarification of such a complex reaction. In this study, d ‐block transition‐metal (TM) anchored C 2 N single layer catalyst is investigated by the density functional theory (DFT) calculation. Both single TM‐anchored single atom catalyst (SAC) and double TM‐anchored double atom catalyst (DAC) exhibit good thermodynamic stability in atomically dispersed catalyst. In the case of SACs, IVB metals (Ti, Zr, Hf) exhibit the highest reactivity and lowest overpotential. While in the case of DACs, Cr─Cr system leads to the NH 3 formation, but V─V system leads to the N 2 H 4 formation. The SACs show much lower overpotential and stronger activation of N 2 molecule than the DACs due to the different activation mechanisms: traditional σ ‐donation/ π ‐backdonation N 2 activation mechanism is found in SACs, while a new π ‐donation/π‐backdonation N 2 activation mechanism is found in the DACs. The present work demonstrates that the different catalytic effect for NRR between SAC and DAC and their corresponding electronic structure origin, which gives more insight into the single atom catalyst. image

Qian, Yumin↗

Single molecule-based fliFISH validates radial and heterogeneous gene expression patterns in pancreatic islet ß cells

Single cell RNA sequencing (scRNA-Seq) technologies have greatly enhanced our understanding of islet cell transcriptomes and have revealed the existence of ß cell heterogeneity. However, comparison of scRNA-Seq datasets from different groups have highlighted inconsistencies in gene expression patterns, primarily due to variable detection of lower abundance transcripts. Furthermore, such analyses are unable to uncover the spatial organization of heterogeneous gene expression. Here we used fluctuation localization imaging-based fluorescence in situ hybridization (fliFISH) to quantify transcripts in single cells in mouse pancreatic islet sections. We compared the expression patterns of Insulin 2 (Ins2) with Mafa and Ucn3 – two genes expressed in ß cells as they mature, as well as Rgs4 – a factor with variably reported expression in the islet. This approach accurately quantified transcripts across a wide range of expression levels - from single copies to over hundred copies per cell in one islet. Importantly, fliFISH allowed evaluation of transcript heterogeneity in the spatial context of an intact islet. These studies confirm the existence of a high degree of heterogeneous gene expression levels within the islet and highlight relative and radial expression patterns that likely reflect distinct ß cell maturation states along the radial axis of the islet.

Li, Fangjia↗

Development of a 0.5 micrometer incoherent Doppler lidar for space application

This paper describes the current status of a prototype 0.53 micrometer Doppler lidar system under development at RCA. This system consists of a frequency doubled Nd:YAG laser constrained to yield a narrow bandwidth, single frequency pulse, a Fabry-Perot Inteferometer (FPI) using an Image Plane Detector (IPD) to measure the backscatter spectrum for each pulse and a Data Acquisition System (DAS) to sample, store, and analyze the backscattered signal. These individual subsystem components have been assembled and preliminary atmospheric testing has recently begun. Atmospheric backscatter spectra are presented which demonstrate the capabilities of this system to distinguish between return signals from aerosols, molecules, and clouds.

Rosenberg, A.↗

Wide-Field Infrared Survey Explorer Observations of the Evolution of Massive Star-Forming Regions

We present the results of a mid-infrared survey of II outer Galaxy massive star-forming regions and 3 open clusters with data from the Wide-field Infrared Survey Explorer (WISE). Using a newly developed photometric scheme to identify young stellar objects and exclude extragalactic contamination, we have studied the distribution of young stars within each region. These data tend to support the hypothesis that latter generations may be triggered by the interaction of winds and radiation from the first burst of massive star formation with the molecular cloud material leftover from that earlier generation of stars. We dub this process the "fireworks hypothesis" since star formation by this mechanism would proceed rapidly and resemble a burst of fireworks. We have also analyzed small cutout WISE images of the structures around the edges of these massive star-forming regions. We observe large (1-3 pc size) pillar and trunk-like structures of diffuse emission nebulosity tracing excited polycyclic aromatic hydrocarbon molecules and small dust grains at the perimeter of the massive star-forming regions. These structures contain small clusters of emerging Class I and Class II sources, but some are forming only a single to a few new stars.

Koenig, X. P.↗

Wide-Field Infrared Survey Explorer Observations of the Evolution of Massive Star-Forming Regions

We present the results of a mid-infrared survey of 11 outer Galaxy massive star-forming regions and 3 open clusters with data from the Wide-field Infrared Survey Explorer (WISE). Using a newly developed photometric scheme to identify young stellar objects and exclude extragalactic contamination, we have studied the distribution of young stars within each region. These data tend to support the hypothesis that latter generations may be triggered by the interaction of winds and radiation from the first burst of massive star formation with the molecular cloud material leftover from that earlier generation of stars.We dub this process the "fireworks hypothesis" since star formation by this mechanism would proceed rapidly and resemble a burst of fireworks.We have also analyzed small cutout WISE images of the structures around the edges of these massive star-forming regions. We observe large (1-3 pc size) pillar and trunk-like structures of diffuse emission nebulosity tracing excited polycyclic aromatic hydrocarbon molecules and small dust grains at the perimeter of the massive star-forming regions. These structures contain small clusters of emerging Class I and Class II sources, but some are forming only a single to a few new stars.

Koenig, X. P.↗

Step-by-step state-selective tracking of fragmentation dynamics of water dications by momentum imaging

Abstract The double photoionization of a molecule by one photon ejects two electrons and typically creates an unstable dication. Observing the subsequent fragmentation products in coincidence can reveal a surprisingly detailed picture of the dynamics. Determining the time evolution and quantum mechanical states involved leads to deeper understanding of molecular dynamics. Here in a combined experimental and theoretical study, we unambiguously separate the sequential breakup via D + + OD + intermediates, from other processes leading to the same D + + D + + O final products of double ionization of water by a single photon. Moreover, we experimentally identify, separate, and follow step by step, two pathways involving the b 1 Σ + and a 1 Δ electronic states of the intermediate OD + ion. Our classical trajectory calculations on the relevant potential energy surfaces reproduce well the measured data and, combined with the experiment, enable the determination of the internal energy and angular momentum distribution of the OD + intermediate.

74 ATOMIC AND MOLECULAR PHYSICS↗

Super-resolution Imaging of Plasmonic Near-Fields: Overcoming Emitter Mislocalizations

Plasmonic nano-objects have shown great potential in enhancing applications like biological/chemical sensing, light harvesting and energy transfer, and optical/quantum computing. Therefore, an extensive effort has been vested in optimizing plasmonic systems and exploiting their field enhancement properties. Super-resolution imaging with quantum dots (QDs) is a promising method to probe plasmonic near-fields but is hindered by the distortion of the QD radiation pattern. Here, we investigate the interaction between QDs and “L-shaped” gold nanoantennas and demonstrate both theoretically and experimentally that this strong interaction can induce polarization-dependent modifications to the apparent QD emission intensity, polarization, and localization. Based on FDTD simulations and polarization-modulated single-molecule microscopy, we show that the displacement of the emitter’s localization is due to the position-dependent interference between the emitter and the induced dipole, and can be up to 100 nm. Our results help pave a pathway for higher precision plasmonic near-field mapping and its underlying applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Array biosensor for detection of toxins

The array biosensor is capable of detecting multiple targets rapidly and simultaneously on the surface of a single waveguide. Sandwich and competitive fluoroimmunoassays have been developed to detect high and low molecular weight toxins, respectively, in complex samples. Recognition molecules (usually antibodies) were first immobilized in specific locations on the waveguide and the resultant patterned array was used to interrogate up to 12 different samples for the presence of multiple different analytes. Upon binding of a fluorescent analyte or fluorescent immunocomplex, the pattern of fluorescent spots was detected using a CCD camera. Automated image analysis was used to determine a mean fluorescence value for each assay spot and to subtract the local background signal. The location of the spot and its mean fluorescence value were used to determine the toxin identity and concentration. Toxins were measured in clinical fluids, environmental samples and foods, with minimal sample preparation. Results are shown for rapid analyses of staphylococcal enterotoxin B, ricin, cholera toxin, botulinum toxoids, trinitrotoluene, and the mycotoxin fumonisin. Toxins were detected at levels as low as 0.5 ng mL(-1).

Review↗

Grism Performance for Mid-IR (5-40 microns) Spectroscopy

Grisms provide a straightforward method to transform an imager into a spectrometer with little change to the original imaging optics. This paper addresses the performance of a suite of grisms as part of an Astrobiology Science and Instrument Development (ASTID) Program to implement a moderate resolution spectroscopic capability to the mid/far-IR facility instrument FORCAST for the Stratospheric Observatory For Infrared Astronomy (SOFIA) [see accompanying abstract by Adams et al.]. A moderate resolution mid-IR spectrometer on SOFIA will offer advantages not available to either ground or space-based instruments after the Spitzer Space Telescope ceases operation in approx. 2007. SOFIA will begin operations in 2007 and will have an operational lifetime of approx. 20 years. From aircraft altitudes, it will be possible to cover a range of wavelengths, particularly in the critical 5-9 micron band, where detection of astrobiologically interesting molecules have key spectral signatures, that are not accessible from the ground. This grism suite consists of six grisms: four monolithic Si grisms [see accompanying abstract by Mar et al.] and two KRS-5 grisms. These devices will allow long slit low-resolution and short slit, cross-dispersed high-resolution spectroscopic modes selectable by simply moving the camera filter wheels. This configuration will enable observing programs to gather images and spectra in a single SOFIA flight. The four silicon grisms, whose performance is highlighted in this paper, will operate in the following wavelength ranges: 5-8, 17-28, and 28-37 microns. In the 5-8 micron range, R=1200 is achievable for a 2 arcsecond slit using the grism as a cross-disperser. For the 17-28 and 28-37 micron ranges, the resolving powers are R approx. 130, 250 when used in low orders with a slit of 3 arcseconds. The silicon grisms demonstrate a new family of dispersive elements with good optical performance for spectroscopy from 1.2-8 micron and beyond 18 microns. Furthermore, the FORCAST grism modes are close in wavelength coverage and resolving power to the Spitzer Infrared Spectrograph (IRS), so that among other possible observations, SOFIA can now enable follow-up studies of the brighter objects that Spitzer has observed and enable studies of sources that were too bright for observation with Spitzer.

Ennico, K. A.↗

Designed and biologically active protein lattices

Versatile methods to organize proteins in space are required to enable complex biomaterials, engineered biomolecular scaffolds, cell-free biology, and hybrid nanoscale systems. Here, we demonstrate how the tailored encapsulation of proteins in DNA-based voxels can be combined with programmable assembly that directs these voxels into biologically functional protein arrays with prescribed and ordered two-dimensional (2D) and three-dimensional (3D) organizations. We apply the presented concept to ferritin, an iron storage protein, and its iron-free analog, apoferritin, in order to form single-layers, double-layers, as well as several types of 3D protein lattices. Our study demonstrates that internal voxel design and inter-voxel encoding can be effectively employed to create protein lattices with designed organization, as confirmed by in situ X-ray scattering and cryo-electron microscopy 3D imaging. The assembled protein arrays maintain structural stability and biological activity in environments relevant for protein functionality. The framework design of the arrays then allows small molecules to access the ferritins and their iron cores and convert them into apoferritin arrays through the release of iron ions. The presented study introduces a platform approach for creating bio-active protein-containing ordered nanomaterials with desired 2D and 3D organizations.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Unveiling the nanoscale architectures and dynamics of protein assembly with in situ atomic force microscopy

Proteins play a vital role in different biological processes by forming complexes through precise folding with exclusive inter- and intra-molecular interactions. Understanding the structural and regulatory mechanisms underlying protein complex formation provides insights into biophysical processes. Furthermore, the principle of protein assembly gives guidelines for new biomimetic materials with potential applications in medicine, energy, and nanotechnology. Atomic force microscopy (AFM) is a powerful tool for investigating protein assembly and interactions across spatial scales (single molecules to cells) and temporal scales (milliseconds to days). It has significantly contributed to understanding nanoscale architectures, inter- and intra-molecular interactions, and regulatory elements that determine protein structures, assemblies, and functions. This review describes recent advancements in elucidating protein assemblies with in situ AFM. We discuss the structures, diffusions, interactions, and assembly dynamics of proteins captured by conventional and high-speed AFM in near-native environments and recent AFM developments in the multimodal high-resolution imaging, bimodal imaging, live cell imaging, and machine-learning-enhanced data analysis. These approaches show the significance of broadening the horizons of AFM and enable unprecedented explorations of protein assembly for biomaterial design and biomedical research.

36 MATERIALS SCIENCE↗

Inferring Stochastic Rates from Heterogeneous Snapshots of Particle Positions

Many imaging techniques for biological systems—like fixation of cells coupled with fluorescence microscopy—provide sharp spatial resolution in reporting locations of individuals at a single moment in time but also destroy the dynamics they intend to capture. In this study, these snapshot observations contain no information about individual trajectories, but still encode information about movement and demographic dynamics, especially when combined with a well-motivated biophysical model. The relationship between spatially evolving populations and single-moment representations of their collective locations is well-established with partial differential equations (PDEs) and their inverse problems. However, experimental data is commonly a set of locations whose number is insufficient to approximate a continuous-in-space PDE solution. Here, motivated by popular subcellular imaging data of gene expression, we embrace the stochastic nature of the data and investigate the mathematical foundations of parametrically inferring demographic rates from snapshots of particles undergoing birth, diffusion, and death in a nuclear or cellular domain. Toward inference, we rigorously derive a connection between individual particle paths and their presentation as a Poisson spatial process. Using this framework, we investigate the properties of the resulting inverse problem and study factors that affect quality of inference. One pervasive feature of this experimental regime is the presence of cell-to-cell heterogeneity. Rather than being a hindrance, we show that cell-to-cell geometric heterogeneity can increase the quality of inference on dynamics for certain parameter regimes. Altogether, the results serve as a basis for more detailed investigations of subcellular spatial patterns of RNA molecules and other stochastically evolving populations that can only be observed for single instants in their time evolution.

59 BASIC BIOLOGICAL SCIENCES↗