Search NASA⌕ Search

SEARCH · Search NASA

Results for “Multiplex”

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 1,207 records · Page 67
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Nanosensor dosimetry of mouse blood proteins after exposure to ionizing radiation

Giant magnetoresistive (GMR) nanosensors provide a novel approach for measuring protein concentrations in blood for medical diagnosis. Using an in vivo mouse radiation model, we developed protocols for measuring Flt3 ligand (Flt3lg) and serum amyloid A1 (Saa1) in small amounts of blood collected during the first week after X-ray exposures of sham, 0.1, 1, 2, 3, or 6 Gy. Flt3lg concentrations showed excellent dose discrimination at $ 1 Gy in the time window of 1 to 7 days after exposure except 1 Gy at day 7. Saa1 dose response was limited to the first two days after exposure. A multiplex assay with both proteins showed improved dose classification accuracy. Our magneto-nanosensor assay demonstrates the dose and time responses, low-dose sensitivity, small volume requirements, and rapid speed that have important advantages in radiation triage biodosimetry.

BIONANOELECTRONICS↗
DOE OSTI2015

Low temperature (550-700 K) oxidation pathways of cyclic ketones: Dominance of HO 2 -elimination channels yielding conjugated cyclic coproducts

The low-temperature oxidation of three cyclic ketones, cyclopentanone (CPO; C 5 H 8 O), cyclohexanone (CHO; C 6 H 10 O), and 2-methyl-cyclopentanone (2-Me-CPO; CH 3 –C 5 H7 O), is studied between 550 and 700 K and at 4 or 8 Torr total pressure. Initial fuel radicals R are formedvia fast H-abstraction from the ketones by laser-photolytically generated chlorine atoms. Intermediates and products from the subsequent reactions of these radicals in the presence of excess O 2 are probed with time and isomeric resolution using multiplexed photoionization mass spectrometry with tunable synchrotron ionizing radiation. For CPO and CHO the dominant product channel in the R + O 2 reactions is chain-terminating HO 2 -elimination yielding the conjugated cyclic coproducts 2-cyclopentenone and 2-cyclohexenone, respectively. Results on oxidation of 2-Me-CPO also show a dominant contribution from HO 2 -elimination. Moreover, the photoionization spectrum of the co-product suggests formation of 2-methyl-2-cyclopentenone and/or 2-cyclohexenone, resulting from a rapid Dowd–Beckwith rearrangement, preceding addition to O 2 , of the initial (2-oxocyclopentyl)methyl radical to 3-oxocyclohexyl. Cyclic ethers, markers for hydroperoxyalkyl radicals (QOOH), key intermediates in chain-propagating and chain-branching low-temperature combustion pathways, are only minor products. The interpretation of the experimental results is supported by stationary point calculations on the potential energy surfaces of the associated R + O 2 reactions at the CBS-QB3 level. Furthermore, the calculations indicate that HO 2 -elimination channels are energetically favored and product formation via QOOH is disfavored. Lastly, the prominence of chain-terminating pathways linked with HO 2 formation in low-temperature oxidation of cyclic ketones suggests little low-temperature reactivity of these species as fuels in internal combustion engines.

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

Spatially uniform resistance switching of low current, high endurance titanium–niobium-oxide memristors

Here we analyzed micrometer-scale titanium-niobium-oxide prototype memristors, which exhibited low write-power (< 3 μW) and energy (< 200 fJ per bit per μm 2 ), low read-power (~nW), and high endurance ( > millions of cycles). To understand their physico-chemical operating mechanisms, we performed in operando synchrotron X-ray transmission nanoscale spectromicroscopy using an ultra-sensitive time-multiplexed technique. We observed only spatially uniform material changes during cell operation, in sharp contrast to the frequently detected formation of a localized conduction channel in transition-metal-oxide memristors. We also associated the response of assigned spectral features distinctly to non-volatile storage (resistance change) and writing of information (application of voltage and Joule heating). Lastly, these results provide critical insights into high-performance memristors that will aid in device design, scaling and predictive circuit-modeling, all of which are essential for the widespread deployment of successful memristor applications.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Ultrastructural and SINS analysis of the cell wall integrity response of Aspergillus nidulans to the absence of galactofuranose

With lethal opportunistic fungal infections on the rise, it is imperative to explore new methods to examine virulence mechanisms. The fungal cell wall is crucial for both the virulence and viability of Aspergillus nidulans. One wall component, Galf, has been shown to contribute to important fungal processes, integrity of the cell wall and pathogenesis. Here in this paper, we explore gene deletion strains lacking the penultimate enzyme in Galf biosynthesis (ugmAΔ) and the protein that transports Galf for incorporation into the cell wall (ugtAΔ). In applying gene deletion technology to the problem of cell wall integrity, we have employed multiple micro- and nano-scale imaging tools, including confocal fluorescence microscopy, electron microscopy, X-Ray fluorescence and atomic force microscopy. Atomic force microscopy allows quantification of ultrastructural cell wall architecture while near-field infrared spectroscopy provides spatially resolved chemical signatures, both at the nanoscale. Here, for the first time, we demonstrate correlative data collection with these two emerging modalities for the multiplexed in situ study of the nanoscale architecture and chemical composition of fungal cell walls.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

Towards Resolving the Spatial Metabolome with Unambiguous Molecular Annotations in Complex Biological Systems by Coupling Mass Spectrometry Imaging with Structures for Lossless Ion Manipulations

We demonstrate the coupling of liquid extraction surface analysis (LESA) to structures for lossless ion manipulations in conjunction with serpentine ultralong path with extending routing (SLIM SUPER) ion mobility-mass spectrometry (IM-MS) for the unambiguous annotation of important isomeric glycoforms in carbon-fixing communities. A major bottleneck of current mass spectrometry imaging (MSI) methods is their inability to accurately and confidently delineate amongst isomers within a single probing area. Our methodology provides gains in both sensitivity and IM resolution, while simultaneously gaining insight on the spatial distribution of these biological isomers in a mixed organism composed of moss, cyanobacteria and fungus. We envision this methodology will be broadly applicable to other mass spectrometry imaging modalities and invaluable in multiplexed, untargeted, analyses of a single probing location.

Nagy, Gabe↗
DOE OSTI2018

Direct kinetics study of CH 2 OO + methyl vinyl ketone and CH 2 OO + methacrolein reactions and an upper limit determination for CH 2 OO + CO reaction

Methyl vinyl ketone (MVK) and methacrolein (MACR) are important intermediate products in atmospheric degradation of volatile organic compounds, especially of isoprene. Here, this work investigates the reactions of the smallest Criegee intermediate, CH 2 OO, with its co-products from isoprene ozonolysis, MVK and MACR, using multiplexed photoionization mass spectrometry (MPIMS), with either tunable synchrotron radiation from the Advanced Light Source or Lyman-α (10.2 eV) radiation for photoionization. CH 2 OO was produced via pulsed laser photolysis of CH 2 I 2 in the presence of excess O 2 . Time-resolved measurements of reactant disappearance and of product formation were performed to monitor reaction progress; first order rate coefficients were obtained from exponential fits to the CH 2 OO decays. The bimolecular reaction rate coefficients at 300 K and 4 Torr are k(CH 2 OO + MVK) = (5.0 ± 0.4) × 10 -13 cm 3 s -1 and k(CH 2 OO + MACR) = (4.4 ± 1.0) × 10 -13 cm 3 s -1 , where the stated ±2σ uncertainties are statistical uncertainties. Adduct formation is observed for both reactions and is attributed to the formation of a secondary ozonides (1,2,4-trioxolanes), supported by master equation calculations of the kinetics and the agreement between measured and calculated adiabatic ionization energies. Kinetics measurements were also performed for a possible bimolecular CH 2 OO + CO reaction and for the reaction of CH 2 OO with CF 3 CHCH 2 at 300 K and 4 Torr. For CH 2 OO + CO, no reaction is observed and an upper limit is determined: k(CH 2 OO + CO) < 2 × 10 -16 cm 3 s -1 . Lastly, for CH 2 OO + CF 3 CHCH 2 , an upper limit of k(CH 2 OO + CF 3 CHCH 2 ) < 2 × 10 -14 cm 3 s -1 is obtained.

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

A universal method for sensitive and cell-free detection of CRISPR-associated nucleases

A multitude of biological applications for CRISPR-associated (Cas) nucleases have propelled the development of robust cell-based methods for quantitation of on- and off-target activities of these nucleases. However, emerging applications of these nucleases require cell-free methods that are simple, sensitive, cost effective, high throughput, multiplexable, and generalizable to all classes of Cas nucleases. Current methods for cell-free detection are cumbersome, expensive, or require sophisticated sequencing technologies, hindering their widespread application beyond the field of life sciences. Developing such cell-free assays is challenging for multiple reasons, including that Cas nucleases are single-turnover enzymes that must be present in large excess over their substrate and that different classes of Cas nucleases exhibit wildly different operating mechanisms. Here, we report the development of a cell-free method wherein Cas nuclease activity is amplified via an in vitro transcription reaction that produces a fluorescent RNA:small-molecule adduct. We demonstrate that our method is sensitive, detecting activity from low nanomolar concentrations of several families of Cas nucleases, and can be conducted in a high-throughput microplate fashion with a simple fluorescent-based readout. We provide a mathematical framework for quantifying the activities of these nucleases and demonstrate two applications of our method, namely the development of a logic circuit and the characterization of an anti-CRISPR protein. We anticipate our method will be valuable to those studying Cas nucleases and will allow the application of Cas nuclease beyond the field of life sciences.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2020

Direct time-resolved detection and quantification of key reactive intermediates in diethyl ether oxidation at T = 450–600 K

High-pressure multiplexed photoionization mass spectrometry (MPIMS) with tunable vacuum ultraviolet (VUV) ionization radiation from the Lawrence Berkeley Labs Advanced Light Source is used to investigate the oxidation of diethyl ether (DEE). Kinetics and photoionization (PI) spectra are simultaneously measured for the species formed. Several stable products from DEE oxidation are identified and quantified using reference PI cross-sections. In addition, we directly detect and quantify three key chemical intermediates: peroxy (ROO˙), hydroperoxyalkyl peroxy (˙OOQOOH), and ketohydroperoxide (HOOP[double bond, length as m-dash]O, KHP). These intermediates undergo dissociative ionization (DI) into smaller fragments, making their identification by mass spectrometry challenging. Furthermore, with the aid of quantum chemical calculations, we identify the DI channels of these key chemical species and quantify their time-resolved concentrations from the overall carbon atom balance at T = 450 K and P = 7500 torr. This allows the determination of the absolute PI cross-sections of ROO˙, ˙OOQOOH, and KHP into each DI channel directly from experiment. The PI cross-sections in turn enable the quantification of ROO˙, ˙OOQOOH, and KHP from DEE oxidation over a range of experimental conditions that reveal the effects of pressure, O 2 concentration, and temperature on the competition among radical decomposition and second O 2 addition pathways.

42 ENGINEERING↗
DOE OSTI2020

Formic acid catalyzed isomerization and adduct formation of an isoprene-derived Criegee intermediate: experiment and theory

Isoprene is the most abundant non-methane hydrocarbon emitted into the Earth's atmosphere. Ozonolysis is an important atmospheric sink for isoprene, which generates reactive carbonyl oxide species (R 1 R 2 C[double bond, length as m-dash]O + O – ) known as Criegee intermediates. This study focuses on characterizing the catalyzed isomerization and adduct formation pathways for the reaction between formic acid and methyl vinyl ketone oxide (MVK-oxide), a four-carbon unsaturated Criegee intermediate generated from isoprene ozonolysis. syn-MVK-oxide undergoes intramolecular 1,4 H-atom transfer to form a substituted vinyl hydroperoxide intermediate, 2-hydroperoxybuta-1,3-diene (HPBD), which subsequently decomposes to hydroxyl and vinoxylic radical products. In this paper, we report direct observation of HPBD generated by formic acid catalyzed isomerization of MVK-oxide under thermal conditions (298 K, 10 torr) using multiplexed photoionization mass spectrometry. The acid catalyzed isomerization of MVK-oxide proceeds by a double hydrogen-bonded interaction followed by a concerted H-atom transfer via submerged barriers to produce HPBD and regenerate formic acid. The analogous isomerization pathway catalyzed with deuterated formic acid (D2-formic acid) enables migration of a D atom to yield partially deuterated HPBD (DPBD), which is identified by its distinct mass (m/z 87) and photoionization threshold. In addition, bimolecular reaction of MVK-oxide with D 2 -formic acid forms a functionalized hydroperoxide adduct, which is the dominant product channel, and is compared to a previous bimolecular reaction study with normal formic acid. Complementary high-level theoretical calculations are performed to further investigate the reaction pathways and kinetics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Primary photodissociation mechanisms of pyruvic acid on S 1 : observation of methylhydroxycarbene and its chemical reaction in the gas phase

Pyruvic acid, a representative alpha-keto carboxylic acid, is one of the few organic molecules destroyed in the troposphere by solar radiation rather than by reactions with free radicals. To date, only its stable final products were identified, often with contribution from secondary chemistry, making it difficult to elucidate photodissociation mechanisms following excitation to the lowest singlet excited-state (S 1 ) and the role of the internal hydrogen bond in the most-stable Tc conformer. Using multiplexed photoionization mass spectrometry we report the first direct experimental evidence, via the observation of singlet methylhydroxycarbene (MHC) following 351 nm excitation, supporting the decarboxylation mechanism previously proposed. Decarboxylation to MHC + CO 2 represents 97–100% of product branching at 351 nm. We observe vinyl alcohol and acetaldehyde, which we attribute to isomerization of MHC. We also observe a 3 ± 2% yield of the Norrish Type I photoproducts CH 3 CO + DOCO, but only from d 1 -pyruvic acid. At 4 Torr pressure, we measure a photodissociation quantum yield of $1.0^{+0}_{–0.4}$, consistent with IUPAC recommendations. However, our measured product branching fractions disagree with IUPAC. In light of previous calculations, these results support a mechanism in which hydrogen transfer on the S 1 excited state occurs at least partially by tunneling, in competition with intersystem crossing to the T 1 state. Here, we present the first evidence of a bimolecular reaction of MHC in the gas phase, where MHC reacts with pyruvic acid to produce a C 4 H 8 O 2 product. This observation implies that some MHC produced from pyruvic acid in Earth's troposphere will be stabilized and participate in chemical reactions with O 2 and H 2 O, and should be considered in atmospheric modeling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Selectively accessing the hotspots of optical nanoantennas by self-aligned dry laser ablation

Plasmonic nanostructures serve as optical antennas for concentrating the energy of incoming light in localized hotspots close to their surface. By positioning nanoemitters in the antenna hotspots, energy transfer is enabled, leading to novel hybrid antenna-emitter-systems, where the antenna can be used to manipulate the optical properties of the nano-objects. The challenge remains how to precisely position emitters within the hotspots. We report a self-aligned process based on dry laser ablation of a calixarene that enables the attachment of molecules within the electromagnetic hotspots at the tips of gold nanocones. Within the laser focus, the ablation threshold is exceeded in nanoscale volumes, leading to selective access of the hotspot areas. A first indication of the site-selective functionalization process is given by attaching fluorescently labelled proteins to the nanocones. In a second example, Raman-active molecules are selectively attached only to nanocones that were previously exposed in the laser focus, which is verified by surface enhanced Raman spectroscopy. Enabling selective functionalization is an important prerequisite e.g. for preparing single photon sources for quantum optical technologies, or multiplexed Raman sensing platforms.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

Time-resolved quantification of key species and mechanistic insights in low-temperature tetrahydrofuran oxidation

Here, we investigate the kinetics and report the time-resolved concentrations of key chemical species in the oxidation of tetrahydrofuran (THF) at 7500 torr and 450–675 K. Experiments are carried out using high-pressure multiplexed photoionization mass spectrometry (MPIMS) combined with tunable vacuum ultraviolet radiation from the Berkely Lab Advanced Light Source. Intermediates and products are quantified using reference photoionization (PI) cross sections, when available, and constrained by a global carbon balance tracking approach at all experimental temperatures simultaneously for the species without reference cross sections. From carbon balancing, we determine time-resolved concentrations for the ROO˙ and ˙OOQOOH radical intermediates, butanedial, and the combined concentration of ketohydroperoxide (KHP) and unsaturated hydroperoxide (UHP) products stemming from the ˙QOOH + O 2 reaction. Furthermore, we quantify a product that we tentatively assign as fumaraldehyde, which arises from UHP decomposition via H 2 O or ˙OH + H loss. The experimentally derived species concentrations are compared with model predictions using the most recent literature THF oxidation mechanism of Fenard et al., (Combust. Flame, 2018, 191, 252–269). Our results indicate that the literature mechanism significantly overestimates THF consumption and the UHP + KHP concentration at our conditions. The model predictions are sensitive to the rate coefficient for the ROO˙ isomerization to ˙QOOH, which is the gateway for radical chain propagating and branching pathways. Comparisons with our recent results for cyclopentane (Demireva et al., Combust. Flame, 2023, 257, 112506) provide insights into the effect of the ether group on reactivity and highlight the need to determine accurate rate coefficients of ROO˙ isomerization and subsequent reactions.

Demireva, Maria↗
DOE OSTI2012

Position and energy-resolved particle detection using phonon-mediated microwave kinetic inductance detectors

We demonstrate position and energy-resolved phonon-mediated detection of particle interactions in a silicon substrate instrumented with an array of microwave kinetic inductance detectors (MKIDs). The relative magnitude and delay of the signal received in each sensor allow the location of the interaction to be determined with < or approx. 1mm resolution at 30 keV. Using this position information, variations in the detector response with position can be removed, and an energy resolution of {sigma}{sub E} = 0.55 keV at 30 keV was measured. Since MKIDs can be fabricated from a single deposited film and are naturally multiplexed in the frequency domain, this technology can be extended to provide highly pixelized athermal phonon sensors for {approx}1 kg scale detector elements. Such high-resolution, massive particle detectors would be applicable to rare-event searches such as the direct detection of dark matter, neutrinoless double-beta decay, or coherent neutrino-nucleus scattering.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2012

A single-shot, multiwavelength electro-optic data-acquisition system for inertial confinement fusion applications (invited)

Electro-optic data-acquisition systems encode the output from voltage-history diagnostics onto optical signals. The optical signals can propagate long distances over fiber-optic links without degrading the bandwidth of the encoded signal while protecting the recording electronics from overvoltage damage. The sinusoidal response and tolerance to high-input voltages of the Mach-Zehnder modulator used for the encoding leads to the additional advantage of a high dynamic range and a reduced need for manually swapping attenuators. We have demonstrated a single-shot, electro-optic data-acquisition system with a 600:1 dynamic range. This system provides optical isolation and a bandwidth of 6 GHz. The prototype system uses multiple optical wavelengths to allow for the multiplexing of up to eight signals onto one photodetector.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2012

Charging effect simulation model used in simulations of plasma etching of silicon

Understanding the consequences of local surface charging on the evolving etching profile is a critical challenge in high density plasma etching. Deflection of the positively charged ions in locally varying electric fields can cause profile defects such as notching, bowing, and microtrenching. We have developed a numerical simulation model capturing the influence of the charging effect over the entire course of the etching process. The model is fully integrated into ViPER (Virtual Plasma Etch Reactor)-a full featured plasma processing simulation software developed at Ilmenau University of Technology. As a consequence, we show that local surface charge concurrently evolves with the feature profile to affect the final shape of the etched feature. Using gas chopping (sometimes called time-multiplexed) etch process for experimental validation of the simulation, we show that the model provides excellent fits to the experimental data and both, bowing and notching effects are captured-as long as the evolving profile and surface charge are simultaneously simulated. In addition, this new model explains that surface scallops, characteristic of gas chopping technique, are eroded and often absent in the final feature profile due to surface charging. The model is general and can be applied across many etching chemistries.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2013

Solid-state framing camera with multiple time frames

A high speed solid-state framing camera has been developed which can operate over a wide range of photon energies. This camera measures the two-dimensional spatial profile of the flux incident on a cadmium selenide semiconductor at multiple times. This multi-frame camera has been tested at 3.1 eV and 4.5 keV. The framing camera currently records two frames with a temporal separation between the frames of 5 ps but this separation can be varied between hundreds of femtoseconds up to nanoseconds and the number of frames can be increased by angularly multiplexing the probe beam onto the cadmium selenide semiconductor.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Merged vector gratings recorded in a photocrosslinkable polymer liquid crystal film for polarimetry

A merged vector grating, which is holographically fabricated in an anisotropic medium by irradiation with interference light with intensity modulation and polarization modulation, was designed to detect the polarization of light. The merged vector grating is recorded by the interference of two elliptically polarized beams with equal intensities, parallel azimuths, equal ellipticities, and different directions of rotation. We clarified theoretically that the Stokes parameters of the incident light beam are described by the diffraction efficiency of the merged vector grating. Also, to apply this property to formation of a polarimeter without any moving parts or mechanisms, two merged vector gratings with different grating vectors were recorded in a photocrosslinkable polymer liquid crystal film by angle-multiplexed holography. By investigation of the diffraction properties of the gratings obtained, we demonstrated the applicability of the merged vector gratings for use in polarimetry.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗