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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 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Resonant acoustic monitoring of damage in plug‐screw feeders

Abstract Plug‐screw feeders are critical in many industrial processes for compressing slurry materials via a rotating plug‐screw feeder. Over time, increasing plug‐screw feeder wear will eventually lead to catastrophic mechanical failure. Early detection of the wear state can prevent unplanned catastrophic failures resulting in operational shut‐downs, costly repairs, and most importantly the health and safety of workers. We present a theoretical basis for a noninvasive, in operando acoustic resonant technique to monitor the wear state of plug‐screw feeders. The technique is based on tracking the resonant acoustic modes of the plug‐screw feeder, which are sensitive to the plug‐screw feeder geometry, material, and operating conditions. We implemented a multivariate polynomial model to estimate the plug‐screw feeder wear state using multiple acoustic resonances by simulating the acoustic resonant modes for two categories of wear (tip and thread damage) that are common in plug‐screw feeders. Fitting multiple resonances to the polynomial model, we demonstrate accurate estimation of the total mass loss, as well as characterization of the type of damage (i.e., tip vs. thread). Current approaches for monitoring plug‐screw feeder wear rely on shutting down the operation and visually inspecting the plug‐screw feeder. The presented acoustic technique offers a noninvasive, in operando measurement approach that mitigates unplanned catastrophic failures. The acoustic resonance technique presented in the paper has a broad range of industrial applications including the Pharmaceutical, Mining, Integrated Biorefineries (IBR), and Additive Manufacturing industries, to name a few.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Synthesis of α,β‐ and β‐Unsaturated Acids and Hydroxy Acids by Tandem Oxidation, Epoxidation, and Hydrolysis/Hydrogenation of Bioethanol Derivatives

Abstract We report a reaction platform for the synthesis of three different high‐value specialty chemical building blocks starting from bio‐ethanol, which might have an important impact in the implementation of biorefineries. First, oxidative dehydrogenation of ethanol to acetaldehyde generates an aldehyde‐containing stream active for the production of C 4 aldehydes via base‐catalyzed aldol‐condensation. Then, the resulting C 4 adduct is selectively converted into crotonic acid via catalytic aerobic oxidation (62 % yield). Using a sequential epoxidation and hydrogenation of crotonic acid leads to 29 % yield of β‐hydroxy acid (3‐hydroxybutanoic acid). By controlling the pH of the reaction media, it is possible to hydrolyze the oxirane moiety leading to 21 % yield of α,β‐dihydroxy acid (2,3‐dihydroxybutanoic acid). Crotonic acid, 3‐hydroxybutanoic acid, and 2,3‐dihydroxybutanoic acid are archetypal specialty chemicals used in the synthesis of polyvinyl‐co‐unsaturated acids resins, pharmaceutics, and bio‐degradable/ ‐compatible polymers, respectively.

Santhanaraj, Daniel↗
DOE OSTI2024

Copper‐Catalyzed C(sp 3 )−H α‐Acetylation: Generation of Quaternary Centers

Abstract α‐substituted ketones are important chemical targets as synthetic intermediates as well as functionalities in natural products and pharmaceuticals. We report the α‐acetylation of C(sp 3 )−H substrates R−H with arylmethyl ketones ArC(O)Me to provide α‐alkylated ketones ArC(O)CH 2 R at RT with t BuOO t Bu as oxidant via copper(I) ‐diketiminato catalysts. Proceeding via alkyl radicals R•, this method enables α‐substitution with bulky substituents without competing elimination that occurs in more traditional alkylation reactions between enolates and alkyl electrophiles. DFT studies suggest the intermediacy of copper(II) enolates [Cu II ](CH 2 C(O)Ar) that capture alkyl radicals R• to give R−CH 2 C(O)Ar outcompeting dimerization of the copper(II) enolate to give the 1,4‐diketone ArC(O)CH 2 CH 2 C(O)Ar.

Okoromoba, Otome E.↗
DOE OSTI2020

Synthesis of α,β‐ and β‐Unsaturated Acids and Hydroxy Acids by Tandem Oxidation, Epoxidation, and Hydrolysis/Hydrogenation of Bioethanol Derivatives

Abstract We report a reaction platform for the synthesis of three different high‐value specialty chemical building blocks starting from bio‐ethanol, which might have an important impact in the implementation of biorefineries. First, oxidative dehydrogenation of ethanol to acetaldehyde generates an aldehyde‐containing stream active for the production of C 4 aldehydes via base‐catalyzed aldol‐condensation. Then, the resulting C 4 adduct is selectively converted into crotonic acid via catalytic aerobic oxidation (62 % yield). Using a sequential epoxidation and hydrogenation of crotonic acid leads to 29 % yield of β‐hydroxy acid (3‐hydroxybutanoic acid). By controlling the pH of the reaction media, it is possible to hydrolyze the oxirane moiety leading to 21 % yield of α,β‐dihydroxy acid (2,3‐dihydroxybutanoic acid). Crotonic acid, 3‐hydroxybutanoic acid, and 2,3‐dihydroxybutanoic acid are archetypal specialty chemicals used in the synthesis of polyvinyl‐co‐unsaturated acids resins, pharmaceutics, and bio‐degradable/ ‐compatible polymers, respectively.

Santhanaraj, Daniel↗
DOE OSTI2020

Nickel–Mediated Trifluoromethylation of Phenol Derivatives by Aryl C–O Bond Activation

The increasing pharmaceutical importance of trifluoromethylarenes has stimulated the development of more efficient trifluoromethylation reactions. Tremendous efforts have focused on copper– and palladium–mediated/catalyzed trifluoromethylation of aryl halides. In contrast, no general method exists for the conversion of widely available inert electrophiles, such as phenol derivatives, into the corresponding trifluoromethylated arenes. Reported herein is a practical nickel–mediated trifluoromethylation of phenol derivatives with readily available trimethyl(trifluoromethyl)silane (TMSCF 3 ). The strategy relies on PMe 3 –promoted oxidative addition and transmetalation, and CCl 3 CN–induced reductive elimination. Here, the broad utility of this transformation has been demonstrated through the direct incorporation of trifluoromethyl into aromatic and heteroaromatic systems, including biorelevant compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Structural and Dynamic Analysis of Sulphur Dioxide Adsorption in a Series of Zirconium-Based Metal–Organic Frameworks

We report reversible high capacity adsorption of SO 2 in robust Zr-based metal–organic framework (MOF) materials. Zr-bptc (H 4 bptc=biphenyl-3,3',5,5'-tetracarboxylic acid) shows a high SO 2 uptake of 6.2 mmol g -1 at 0.1 bar and 298 K, reflecting excellent capture capability and removal of SO 2 at low concentration (2500 ppm). Dynamic breakthrough experiments confirm that the introduction of amine, atomically-dispersed Cu II or heteroatomic sulphur sites into the pores enhance the capture of SO 2 at low concentrations. The captured SO 2 can be converted quantitatively to a pharmaceutical intermediate, aryl N-aminosulfonamide, thus converting waste to chemical values. In situ X-ray diffraction, infrared micro-spectroscopy and inelastic neutron scattering enable the visualisation of the binding domains of adsorbed SO 2 molecules and host–guest binding dynamics in these materials at the atomic level. Refinement of the pore environment plays a critical role in designing efficient sorbent materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Copper‐Catalyzed C(sp 3 )−H α‐Acetylation: Generation of Quaternary Centers

Abstract α‐substituted ketones are important chemical targets as synthetic intermediates as well as functionalities in natural products and pharmaceuticals. We report the α‐acetylation of C(sp 3 )−H substrates R−H with arylmethyl ketones ArC(O)Me to provide α‐alkylated ketones ArC(O)CH 2 R at RT with t BuOO t Bu as oxidant via copper(I) ‐diketiminato catalysts. Proceeding via alkyl radicals R•, this method enables α‐substitution with bulky substituents without competing elimination that occurs in more traditional alkylation reactions between enolates and alkyl electrophiles. DFT studies suggest the intermediacy of copper(II) enolates [Cu II ](CH 2 C(O)Ar) that capture alkyl radicals R• to give R−CH 2 C(O)Ar outcompeting dimerization of the copper(II) enolate to give the 1,4‐diketone ArC(O)CH 2 CH 2 C(O)Ar.

Okoromoba, Otome E.↗
DOE OSTI2025

Radical Borylation of Alkyl Bromides by Photoinduced Halogen‐Atom Transfer

Alkyl organoboron compounds are versatile synthons in organic synthesis, enabling rapid access to a variety of carbon─carbon and carbon-heteroatom bonds. As such, strategies to efficiently access carbon-boron bonds from simple chemical feedstocks are highly desirable. The radical borylation of alkyl bromides presents an attractive approach. However, the activation of alkyl bromides typically requires strong reductants or transition-metal catalysts. Herein, we report a metal-free radical borylation strategy of various alkyl bromides utilizing a photoinduced silyl radical to mediate a halogen-atom transfer process. This method demonstrates broad utility and functional group tolerance among various primary, secondary, and tertiary unactivated alkyl bromides and can facilitate the functionalization of pharmaceutically relevant motifs. Mechanistic and computational studies support a radical-chain pathway involving a silyl radical-mediated halogen-atom transfer.

Alkyls↗
DOE OSTI2021

L–malic acid production from xylose by engineered Saccharomyces cerevisiae

L-malic acid is widely used in the food, chemical, and pharmaceutical industries. Here, we report on production of malic acid from xylose, the second most abundant sugar in lignocellulosic hydrolysates, by engineered Saccharomyces cerevisiae. To enable malic acid production in a xylose-assimilating S. cerevisiae, we overexpressed PYC1 and PYC2, coding for pyruvate carboxylases, a truncated MDH3 coding for malate dehydrogenase, and SpMAE1, coding for a Schizosaccharomyces pombe malate transporter. Additionally, both the ethanol and glycerol-producing pathways were blocked to enhance malic acid production. The resulting strain produced malic acid from both glucose and xylose, but it produced much higher titers of malic acid from xylose than glucose. Interestingly, the engineered strain had higher malic acid yield from lower concentrations (10 g L –1 ) of xylose, with no ethanol production, than from higher xylose concentrations (20 and 40 g L –1 ). As such, a fed-batch culture maintaining xylose concentrations at low levels was conducted and 61.2 g L –1 of malic acid was produced, with a productivity of 0.32 g L –1 h. Furthermore, these results represent successful engineering of S. cerevisiae for the production of malic acid from xylose, confirming that that xylose offers the efficient production of various biofuels and chemicals by engineered S. cerevisiae.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Acetaminophen production in the edible, filamentous cyanobacterium Arthrospira platensis

Abstract Spirulina is the common name for the edible, nonheterocystous, filamentous cyanobacteriumArthrospira platensisthat is grown industrially as a food supplement, animal feedstock, and pigment source. Although there are many applications for engineering this organism, until recently no genetic tools or reproducible transformation methods have been published. While recent work showed the production of a diversity of proteins inA. platensis, including single‐domain antibodies for oral delivery, there remains a need for a modular, characterized genetic toolkit. Here, we independently establish a reproducible method for the transformation ofA. platensisand engineer this bacterium to produce acetaminophen as proof‐of‐concept for small molecule production in an edible host. This work opensA. platensisto the wider scientific community for future engineering as a functional food for nutritional enhancement, modification of organoleptic traits, and production of pharmaceuticals for oral delivery.

Biotechnology & Applied Microbiology↗
DOE OSTI2020

Selectivity Control in Catalytic Reductive Amination of Furfural to Furfurylamine on Supported Catalysts

Abstract Amines are widely used in the manufacture of pharmaceuticals, agricultural chemicals, polymers, and surfactants. However, amines are mostly produced via petrochemical means, which motivates amine production from renewable resources, such as biomass. However, biomass compounds present added challenges involving poor carbon balances. We show that furfural reacts homogeneously with ammonia to produce reactive primary imines, which form large side products and leads to significant carbon losses. The carbon balance is improved by mixing furfural with furfurylamine prior to reaction to form a secondary imine for use as the reaction substrate. While controlling the primary to secondary amine selectivity is a common challenge in reductive amination, supported metal catalysts, including Ni/SiO 2 , Co/SiO 2 , and Ru/SiO 2 optimize the primary amine yield to 90 to 94 % by using the secondary imine as the reaction substrate. A qualitative correlation between the primary to secondary amine selectivity with the nitrogen binding energy of metals is identified.

Gould, Nicholas S.↗
DOE OSTI2023

Precise Control of Dissipative Self-assembly by Light and Electricity

Nature-inspired synthetic dissipative self-assemblies have attracted much attention recently. However, it remains a major challenge to achieve precise control over dissipative supramolecular assembly structures and functions of self-contained systems. Here we combine light and electricity as two clean, and spatiotemporally addressable fuels to provide precise control over the morphology for dissipative self-assembly of a perylene bisimide glycine (PBIg) building block in a self-contained solution. In this design, electrochemical oxidation provides the positive fuel to activate PBIg self-assembly while photoreduction supplies the negative fuel to deactivate the system for disassembly. Further, through programming the two counteracting fuels, we demonstrated the control of PBIg self-assembly into a variety of assembly morphologies in a self-contained system. In addition, by exerting light and electrical dual fuels simultaneously, we could create an active homeostasis exhibiting dynamic instability, leading to morphological change to asymmetric assemblies with curvatures. Such precise control over self-assembly of self-contained systems may find future applications in programming complex active materials as well as formulating pharmaceutical reagents with desired morphologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Probing Noncovalent Interaction Strengths of Host-Guest Complexes Using Negative Ion Photoelectron Spectroscopy

Noncovalent interactions (NCIs) are crucial for the formation and stability of host-guest complexes, which have wide-ranging implications across various fields, including biology, chemistry, materials science, pharmaceuticals, and environmental science. However, since NCIs are relatively weak and sensitive to bulk perturbation, direct and accurate measurement of their absolute strength has always been a significant challenge. This concept article aims to demonstrate the gas-phase electrospray ionization (ESI)-negative ion photoelectron spectroscopy (NIPES) as a direct and precise technique to measure the absolute interaction strength, probe nature of NCIs, and reveal the electronic structural information for host-guest complexes. Here, our recent studies in investigating various host-guest complexes that involve various types of NCIs such as anion–π, (di)hydrogen bonding, charge-separated ionic interactions, are overviewed. Finally, a summary and outlook are provided for this field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Oxidative Dehydrogenation of N ‐Heteroaromatic Alkyl Alcohols and Amines Facilitated by Dearomative Tautomerization

The oxidation of alcohols, amines, and halides is a fundamental transformation in organic chemistry with significant applications in the synthesis of fine chemicals, pharmaceuticals, and natural products. Here we show that a broad variety of N-heteroarenes bearing hydroxymethyl, aminomethyl, or halomethyl groups are oxidatively dehydrogenated to their respective aldehydes by simply heating them in acidic or basic aqueous solution under ambient atmosphere. The quantitative oxidation of 9-acridinemethanol to 9-acridinecarboxaldehyde serves as an illustrative example, proceeding to completion within 3 hours in refluxing 5% aqueous acetic acid or even household vinegar. Quinoline derivatives may be similarly oxidized but require higher temperatures and longer reaction times, while indole derivatives are oxidized under basic conditions. Based on comprehensive regioselectivity screens, internal kinetic isotope competition, and density functional theory (DFT) calculations, we propose a mechanism in which migration of a methylene hydrogen to the pyridinic nitrogen by acid-catalyzed dearomative tautomerization yields an unstable enol or enamine intermediate that then irreversibly loses two hydrogen atoms to atmospheric oxygen. In addition to the simplicity and environmentally benign nature of our method, we observe no indication of any over-oxidation to carboxylic acids. Finally, we demonstrate the synthetic utility of this reaction through two different one-pot formylations of acridine.

Chemistry↗
DOE OSTI2025

Designing Cyclic Nitrogen‐Bridged Sulfonamides with Anti‐Cancer Activity

The N-bridgehead heterocyclic structure is an abundant motif in a multitude of natural products. This structural feature is of high interest because it is present in many different bioactive molecules, many of which are well-established pharmaceuticals. The introduction of a sulfone group into the N-bridgehead system yields a new core structure containing a N-bridgehead sulfonamide. While linear sulfonamides can be found in natural products, only artificial cyclic sulfonamides are known to date. Applications of related cyclic sulfonamide compounds include matrix metalloproteinase inhibitors, potential HIV and cancer therapeutics, and anti-inflammatory compounds. To explore the potential bioactivity of the N-bridgehead sulfonamide scaffold, a synthetic route toward these scaffolds is developed and their bioactivity is explored against different cancer cell lines.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2020

2D Ising Model for Adsorption–induced Enantiopurification of Racemates

Mechanisms for the spontaneous transformation of achiral chemical systems into states of enantiomeric purity have important ramifications in modern pharmacology and potential relevance to the origins of homochirality in life on Earth. Such mechanisms for enantiopurification are needed for production of chiral pharmaceuticals and other bioactive compounds. Previously proposed chemical mechanisms leading from achiral systems to near homochirality are initiated by a symmetry–breaking step resulting in a minor excess of one enantiomer via statistical fluctuations in enantiomer concentrations. Subsequent irreversible processes then amplify the majority enantiomer concentration while simultaneously suppressing minority enantiomer production. Herein, equilibrium adsorption of amino acid enantiomer mixtures onto chiral and achiral surfaces reveals amplification of surface enantiomeric excess relative to the gas phase; i. e. enantiopurification of chiral adsorbates by adsorption. Furthermore, this adsorption–induced amplification of enantiomeric excess is shown to be well–describe by the 2D Ising model. More importantly, the 2D–Ising model predicts formation of homochiral monolayers from adsorption of racemic mixtures or prochiral molecules on achiral surfaces; i.e. enantiopurification with no apparent chiral driving force.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Methodology for Good Machine Learning with Multi‐Omics Data

In 2020, Novartis Pharmaceuticals Corporation and the U.S. Food and Drug Administration (FDA) started a 4‐year scientific collaboration to approach complex new data modalities and advanced analytics. The scientific question was to find novel radio‐genomics‐based prognostic and predictive factors for HR+/HER− metastatic breast cancer under a Research Collaboration Agreement. This collaboration has been providing valuable insights to help successfully implement future scientific projects, particularly using artificial intelligence and machine learning. This tutorial aims to provide tangible guidelines for a multi‐omics project that includes multidisciplinary expert teams, spanning across different institutions. We cover key ideas, such as “maintaining effective communication” and “following good data science practices,” followed by the four steps of exploratory projects, namely (1) plan, (2) design, (3) develop, and (4) disseminate. We break each step into smaller concepts with strategies for implementation and provide illustrations from our collaboration to further give the readers actionable guidance.

Pharmacology & Pharmacy↗
DOE OSTI2024

Production of Biomass–Derived p –Hydroxybenzamide: Synthesis of p –Aminophenol and Paracetamol

As we work to transition the modern society that is based on non-renewable chemical feedstocks to a post-modern society built around renewable sources of energy, fuels, and chemicals, there is a need to identify the renewable resources and processes for converting them to platform chemicals. Herein, we explore a strategy for utilizing the p-hydroxybenzoate in biomass feedstocks (e.g., poplar and palm trees) and converting it into a portfolio of commodity chemicals. The targeted bio-derived product in the first processing stage is p-hydroxybenzamide produced from p-hydroxybenzoate esters found in the plant. In the second stage a continuous reaction process converts the p-hydroxybenzamide to p-aminophenol via the Hofmann rearrangement and recovers the unreacted p-hydroxybenzamide. In the third stage the p-aminophenol can be acetylated to form paracetamol, which is readily isolated by liquid/liquid extraction at >95 % purity and an overall p-hydroxybenzamide-to-paracetamol process yield of ~90 %. We explore how utilization of protecting groups alters the challenges in this process and expands the portfolio of possible products to include p-(methoxymethoxy)aniline and N-acetyl-p-(methoxymethoxy)aniline. These target compounds could become value-added renewably-sourced platform chemicals that could be used to produce biodegradable plastics, pigments, and pharmaceuticals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗