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NASA NTRS2006

Oxygen-Permeable, Hydrophobic Membranes of Silanized alpha-Al2O3

Membranes made of silanized alumina have been prepared and tested as prototypes of derivatized ceramic membranes that are both highly permeable to oxygen and hydrophobic. Improved oxygen-permeable, hydrophobic membranes would be attractive for use in several technological disciplines, including supporting high-temperature aqueousphase oxidation in industrial production of chemicals, oxygenation of aqueous streams for bioreactors, and oxygenation of blood during open-heart surgery and in cases of extreme pulmonary dysfunction. In comparison with organic polymeric oxygen-permeable membranes now commercially available, the derivatized ceramic membranes are more chemically robust, are capable of withstanding higher temperatures, and exhibit higher oxygen-diffusion coefficients.

Atwater, James E.↗

NASA NTRS2013

Detection of Organics at Mars: How Wet Chemistry Onboard SAM Helps

For the first time in the history of space exploration, a mission of interest to astrobiology could be able to analyze refractory organic compounds in the soil of Mars. Wet chemistry experiment allow organic components to be altered in such a way that improves there detection either by releasing the compounds from sample matricies or by changing the chemical structure to be amenable to analytical conditions. The latter is particular important when polar compounds are present. Sample Analysis at Mars (SAM), on the Curiosity rover of the Mars Science Laboratory mission, has onboard two wet chemistry experiments: derivatization and thermochemolysis. Here we report on the nature of the MTBSTFA derivatization experiment on SAM, the detection of MTBSTFA in initial SAM results, and the implications of this detection.

astrobiology↗

NASA NTRS2017

A Fast, Accurate and Sensitive GC-FID Method for the Analyses of Glycols in Water and Urine

Glycols, specifically ethylene glycol and 1,2-propanediol, are some of the major organic compounds found in the humidity condensate samples collected on the International Space Station. The current analytical method for glycols is a GC/MS method with direct sample injection. This method is simple and fast, but it is not very sensitive. Reporting limits for ethylene glycol and 1,2-propanediol are only 1 ppm. A much more sensitive GC/FID method was developed, in which glycols were derivatized with benzoyl chloride for 10 minutes before being extracted with hexane. Using 1,3-propanediol as an internal standard, the detection limits for the GC/FID method was determined to be 50 ppb and the analysis only takes 7 minutes. Data from the GC/MS and the new GC/FID methods shows excellent agreement with each other. Factors affecting the sensitivity, including sample volume, NaOH concentration and volume, volume of benzoyl chloride, reaction time and temperature, were investigated. Interferences during derivatization and possible method to reduce interferences were also investigated.

Kuo, C. Mike↗

NASA NTRS2023

Evaluation of the Interference of Tenax®TA Adsorbent With Dimethylformamide Dimethyl Acetal Reagent for Gas Chromatography-Dragonfly Mass Spectrometry and Future Gas Chromatography-Mass Spectrometry in Situ Analysis

Among future space missions, national aeronautics and space administration (NASA) selected two of them to analyze the diversity in organic content within Martian and Titan soil samples using a gas chromatograph – mass spectrometer (GC–MS) instrument. The Dragonfly space mission is planned to be launched in 2027 to Titan's surface and explore the Shangri-La surface region for years. One of the main goals of this mission is to understand the past and actual abundant prebiotic chemistry on Titan, which is not well characterized yet. The ExoMars space mission is planned to be launched in 2028 to Mars’ surface and explore the Oxia Planum and Mawrth Vallis region for years. The main objectives focus on the exploration of the subsurface soil samples, potentially richer in organics, that might be relevant for the search of past life traces on Mars where irradiation does not impact the matrices and organics. One recently used sample pre-treatment for gas chromatography – mass spectrometry analysis is planned on both space missions to detect refractory organic molecules of interest for astrobiology. This pre-treatment is called derivatization and uses a chemical reagent – called dimethylformamide dimethyl acetal (DMF-DMA) – to sublimate organic compounds keeping them safe from thermal degradation and conserving the chirality of the molecules extracted from Titan or Mars’ matrices. Indeed, the detection of building blocks of life or enantiomeric excess of some organics (e.g. amino acids) after DMF-DMA pre-treatment and GC–MS analyses would be both bioindicators. The main results highlighted by our work on DMF-DMA and Tenax®TA interaction and efficiency to detect organic compounds at ppb levels in a fast and single preparation are first that Tenax®TA did not show the onset of degradation until after 150 experiments – a 120 h at 300 °C experiment – which greatly exceeds the experimental lifetimes for the DraMS and GC-space in situ investigations. Tenax®TA polymer and DMF-DMA produce many by-products (about 70 and 46, respectively, depending on the activation temperature). Further, the interaction between the two leads to the production of 22 additional by-products from DMF-DMA degradation, but these listed by-products do not prevent the detection of trace-level organic molecules after their efficient derivatization and volatilization by DMF-DMA in the oven ahead the GC–MS trap and column.

DraMS-Dragonfly mission↗

DOE OSTI2021

Solid phase sampling device and methods for point-source sampling of polar organic analytes

Sampling devices for sampling an aqueous source (e.g., field testing of ground water) for multiple different analytes are described. Devices include a solid phase extraction component for retention of a wide variety of targeted analytes. Devices include analyte derivatization capability for improved extraction of targeted analytes. Thus, a single device can be utilized to examine a sample source for a wide variety of analytes. Devices also include an isotope dilution capability that can prevent error introduction to the sample analysis and can correct for sample loss and degradation from the point of sampling until analysis as well as correction for incomplete or poor derivatization reactions. The devices can be field-deployable and rechargeable.

Boggess, Andrew J.↗

DOE OSTI2023

Solid-phase sampling device and methods for point-source sampling of polar organic analytes

Boggess, Andrew J.↗

DOE OSTI2023

Ene Reductase Enabled Intramolecular β–C–H Functionalization of Substituted Cyclohexanones for Efficient Synthesis of Bridged Bicyclic Nitrogen Scaffolds

Herein we report that ene reductases (EREDs) can facilitate an unprecedented intramolecular β-C–H functionalization reaction for the synthesis of bridged bicyclic nitrogen heterocycles containing the 6-azabicyclo[3.2.1]octane scaffold. To streamline the synthesis of these privileged motifs, we developed a gram-scale one-pot chemoenzymatic cascade by combining iridium photocatalysis with EREDs, using readily available N-phenylglycines and cyclohexenones that can be obtained from biomass. Further derivatization using enzymatic or chemical methods can convert 6-azabicyclo[3.2.1]octan-3-one into 6-azabicyclo[3.2.1]octan-3α-ols, which can be potentially utilized for the synthesis of azaprophen and its analogues for drug discovery. Furthermore, mechanistic studies revealed the reaction requires oxygen, presumably to produce oxidized flavin, which can selectively dehydrogenate the 3-substituted cyclohexanone derivatives to form the α,β-unsaturated ketone, which subsequently undergoes spontaneous intramolecular aza-Michael addition under basic conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Ene Reductase Enabled Intramolecular β–C–H Functionalization of Substituted Cyclohexanones for Efficient Synthesis of Bridged Bicyclic Nitrogen Scaffolds

Herein we report that ene reductases (EREDs) can facilitate an unprecedented intramolecular β-C–H functionalization reaction for the synthesis of bridged bicyclic nitrogen heterocycles containing the 6-azabicyclo[3.2.1]octane scaffold. To streamline the synthesis of these privileged motifs, we developed a gram-scale one-pot chemoenzymatic cascade by combining iridium photocatalysis with EREDs, using readily available N-phenylglycines and cyclohexenones that can be obtained from biomass. Further derivatization using enzymatic or chemical methods can convert 6-azabicyclo[3.2.1]octan-3-one into 6-azabicyclo[3.2.1]octan-3α-ols, which can be potentially utilized for the synthesis of azaprophen and its analogues for drug discovery. Here, mechanistic studies revealed the reaction requires oxygen, presumably to produce oxidized flavin, which can selectively dehydrogenate the 3-substituted cyclohexanone derivatives to form the α,β-unsaturated ketone, which subsequently undergoes spontaneous intramolecular aza-Michael addition under basic conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Structure–Activity Relationships of Inactive‐Conformation Binding EGFR Inhibitors: Linking the ATP and Allosteric Pockets

ABSTRACT The epidermal growth factor receptor (EGFR) tyrosine kinase is an important therapeutic target in non‐small cell lung cancer (NSCLC). However, the continual emergence of resistance mutations in the treatment of EGFR mutation‐positive NSCLC with currently approved tyrosine kinase inhibitors warrants the development of next‐generation inhibitors. Since research for ATP‐competitive EGFR tyrosine kinase inhibitors (TKIs) that extend into the back pocket has been neglected in the recent past, we survey the extent to which such binding functional groups can be incorporated into an ATP‐site imidazole scaffold. We find thatmeta‐substituted amide linkers derivatized with fluorine in 2,6‐positions and/or a hydroxy group in 3‐position of the back pocket phenyl exhibit the highest potency. Structural insights into how the back pocket groups are bound through points of connection provide new directions for the discovery and optimization of inactive conformation targeting agents in EGFR and other kinases.

Chemistry↗

DOE OSTI2020

Hybrid Carbon Dioxide Reduction Photocatalysts Consisting of Macrocyclic Cobalt(III) Complexes Deposited on Semiconductor Surfaces

Hybrid photocatalysts can be prepared by coupling metal ligand complexes with light-harvesting semiconductors. It is often challenging and time consuming to derivatize ligands with anchoring groups to effectively attach onto surfaces. In this study, we synthesized hybrid carbon dioxide reduction photocatalysts by directly depositing two macrocyclic Co(III) complexes on three different semiconductor surfaces (TiO 2 , N-Ta 2 O 5 and C 3 N 4 ). The resulting hybrid photocatalysts were characterized with various techniques and tested in CO 2 reduction reactions under different light conditions. Excellent visible-light CO 2 -reduction activity was obtained using C 3 N 4 as the light-harvesting semiconductor. Furthermore, density functional theory calculations were conducted to help understand interactions between the cobalt complexes with a model TiO 2 surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Quantitative Low-Field 19 F Nuclear Magnetic Resonance Analysis of Carbonyl Groups in Pyrolysis Oils

Pyrolysis bio-oils, one of the products of lignocellulosic biomass pyrolysis, have the potential to be widely used as fuels. The chemical composition of bio-oils is very complicated as they contain hundreds, if not thousands, of different, mostly oxygen-containing, compounds with a wide distribution of physical properties, chemical structures, and concentrations. Detailed knowledge of bio-oil composition is crucial for optimizing both the pyrolysis processes and for any subsequent upgrading into a more viable fuel resource. Here we report the successful use of low-field, or benchtop, nuclear magnetic resonance (NMR) spectrometers in the analysis of pyrolysis oils. Pyrolysis oils from four different feedstocks were derivatized and analyzed using 19 F NMR techniques. The NMR results compare favorably with titrations for total carbonyl content. In addition, the benchtop NMR spectrometer proves able to reveal key spectral features, thus allowing the quantification of different carbonyl groups, such as aldehydes, ketones and quinones. Benchtop NMR spectrometers are typically compact, cheaper than their superconducting counterparts and do not require cryogens. Their use will make NMR analysis of pyrolysis oils easier and more accessible to a wide range of different potential users.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Synthesis and Structural Characterization of 2′‐Deoxy‐2′‐Methoxy‐ L ‐Cytidine Nucleic Acids

Abstract We report here for the first time the synthesis of a novel 2′‐methoxy‐modified L‐cytidine analog and its phosphoramidite, as well as its incorporation into oligonucleotides via solid‐phase synthesis. Our measure the thermostability of the modified L‐nucleic acids by UV‐melting studies, and find out the 2′‐methoxy‐derivatization enhances the thermostability of the L‐duplexes. Consistent with the thermostability result, our X‐ray crystal structure study reveals that the 2′‐methoxy‐L‐deoxycytidine forms the Watson‐Crick base pair with L‐guanosine virtually as the mirror‐image fashion of native pair. This novel chemically modified L‐cytidine provides a useful biochemical and structural strategy to create mirror‐image nucleic acid molecules with expanded functionalities.

2′-Methoxy↗

DOE OSTI2023

Synthesis of Pyrimidine Modified Seleno–DNA as a Novel Approach to Antisense Candidate

Chemically modified antisense oligonucleotides (ASO) currently in pre–clinical and clinical experiments mainly focus on the 2’–position derivatizations to enhance stability and targeting affinity. Considering the possible incompatibility of 2’–modifications with RNase H stimulation and activity, we have hypothesized that the atom specific modifications on nucleobases can retain the complex structure and RNase H activity, while enhancing ASO's binding affinity, specificity, and stability against nucleases. Herein we report a novel strategy to explore our hypothesis by synthesizing the deoxynucleoside phosphoramidite building block with the seleno–modification at 5–position of thymidine, as well as its Se–oligonucleotides. Via X–ray crystal structural study, we found that the Se–modification was located in the major groove of nucleic acid duplex and didn't cause the thermal and structural perturbations. Surprisingly, our nucleobase–modified Se–DNAs were exceptionally resistant to nuclease digestion, while compatible with RNase H activity. In conclusion, this affords a novel avenue for potential anti–sense modification in the form of Se–antisense oligonucleotides (Se–ASO).

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DOE OSTI2023

Elucidating the speciation of extracted lanthanides by diglycolamides

Many studies over the past few decades have been devoted to addressing the application of diglycolamides (DGAs) for hydrometallurgical-based, f-element separations. Work to date has shown the molecular structure of a DGA derivative can have a significant impact on intra-lanthanide partitioning patterns. More recent studies have pushed towards probing the structure function relationship of the lanthanide-DGA complex to enable the design of more efficient lanthanide separation systems. Spectroscopic techniques, such as UV–Visible, Fourier Transformed Infrared Spectroscopy (FT-IR), Nuclear Magnetic Resonance (NMR), and Extended X-ray Absorption Fine Structure (EXAFS), provide information regarding the inner-sphere coordination of a given lanthanide-DGA complex. Scattering techniques, such as Dynamic Light Scattering (DLS), Small-Angle X-ray Scattering (SAXS), and Small-Angle Neutron Scattering (SANS), address nanoscale structures including aggregate sizes and morphology. Here, this review assesses the current state-of-knowledge regarding lanthanide-DGA hydrometallurgical (i.e., solvent extraction systems) interrogated using spectroscopic and scattering techniques to characterize the extracted Ln 3+ DGA species. Of particular interest to this review is the impact of varied diluents, inclusion and variation of phase modifiers, and DGA derivatization on system characteristics. While there has been extensive literature on the application of DGAs for f-element separations, the literature lacks a collective assessment of the speciation of Ln 3+ in the organic phase. This review provides new insights into the field of DGA separations, explicitly with an application to intra-lanthanide separations. Specifically, this review illustrates the importance of both the co-extraction anion (Cl - , NO 3 - , or ClO 4 - ) as it pertains to both the aggregate size and Ln 3+ distribution coefficient. It is evident the ability of the anion to disrupt the hydrogen bonding network limits both aggregate size and distribution coefficients according to the Hoffmeister series. This suggests the importance of the large, softer anions with a low charge-to-surface area ratio on encouraging hydrogen bond interactions. In addition, the co-extracted cation (H + vs Na + ) is important for mitigating transfer of Ln 3+ from the aqueous to the organic phase through extensive hydrogen bonding networks. These networks are responsible for forming supramolecular aggregates where a change in morphology is observed with increasing concentrations of H + and/or Ln 3+ in the organic phase.

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DOE OSTI2021

Synthesis of N-trifluoromethyl amides from carboxylic acids

Found in biomolecules, pharmaceuticals, and agrochemicals, amide-containing molecules are ubiquitous in nature, and their derivatization represents a significant methodological goal in fluorine chemistry. Trifluoromethyl amides have emerged as important functional groups frequently found in pharmaceutical compounds. To date, there is no strategy for synthesizing N -trifluoromethyl amides from abundant organic carboxylic acid derivatives, which are ideal starting materials in amide synthesis. Here, we report the synthesis of N -trifluoromethyl amides from carboxylic acid halides and esters under mild conditions via isothiocyanates in the presence of silver fluoride at room temperature. Through this strategy, isothiocyanates are desulfurized with AgF, and then the formed derivative is acylated to afford N -trifluoromethyl amides, including previously inaccessible structures. This method shows broad scope, provides a platform for rapidly generating N -trifluoromethyl amides by virtue of the diversity and availability of both reaction partners, and should find application in the modification of advanced intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Chemical changes in thirdhand smoke associated with remediation using an ozone generator

Ozonation is a common remediation approach to eliminate odors from mold, tobacco and fire damage in buildings. Little information exists to: 1) assess its effectiveness; 2) provide guidance on operation conditions; and 3) identify potential risks associated with the presence of indoor ozone and ozonation byproducts. The goal of this study is to evaluate chemical changes in thirdhand smoke (THS) aerosols induced by high levels of ozone, in comparison with THS aerosols aged under similar conditions in the absence of ozone. Samples representing different stages of smoke aging in the absence of ozone, including freshly emitted secondhand smoke (SHS) and THS, were collected inside an 18-m 3 room-sized chamber over a period of 42 h after six cigarettes were consumed. The experiments involved collection and analysis of gas phase species including volatile organic compounds (VOCs), volatile carbonyls, semivolatile organic compounds (SVOCs), and particulate matter. VOC analysis was carried out by gas chromatography/mass spectrometry with a thermal desorption inlet (TD-GC/MS), and volatile carbonyls were analyzed by on-line derivatization with dinitrophenylhydrazine (DNPH), followed by liquid chromatography with UV/VIS detection. SVOCs were extracted from XAD-coated denuders and Teflon-coated fiberglass filters in the absence of ozone. In those extracts, tobacco-specific nitrosamines (TSNAs) and other SVOCs were analyzed by gas chromatography with positive chemical ionization-triple quadrupole mass spectrometric detection (GC/PCI-QQQ-MS), and polycyclic aromatic hydrocarbons (PAHs) were quantified by gas chromatography with ion trap mass spectrometric detection (GC/IT-MS) in selected ion monitoring mode. Particulate matter concentration was determined gravimetrically. In a second experiment, a 300 mg h -1 commercial ozone generator was operated during 1 h, one day after smoke was generated, to evaluate the remediation of THS by ozonation. VOCs and volatile carbonyls were analyzed before and after ozonation. Extracts from fabrics that were exposed in the chamber before and after ozonation as surrogates for indoor furnishings were analyzed by GC/IT-MS, and aerosol size distribution was studied with a scanning mobility particle sizer. Ozone concentration was measured with a photometric detector. An estimated 175 mg ozone reacted with THS after 1 h of treatment, corresponding to 58% of the total O 3 released during that period. Fabric-bound nicotine was depleted after ozonation, and the surface concentration of PAHs adsorbed to fabric specimens decreased by an order of magnitude due to reaction with ozone, reaching pre-smoking levels. These results suggest that ozonation has the potential to remove harmful THS chemicals from indoor surfaces. However, gas phase concentrations of volatile carbonyls, including formaldehyde, acetaldehyde and acetone were higher immediately after ozonation. Ultrafine particles (UFP, in most cases with size <60 nm) were a major ozonation byproduct. UFP number concentrations peaked shortly after ozonation ended, and remained at higher-than background levels for several hours. Based on these results, minimum re-entry times after ozone treatment were predicted for different indoor scenarios. Clearly defining re-entry times can serve as a practical measure to prevent acute exposures to ozone and harmful ozonation byproducts after treatment. This study evaluated potential benefits and risks associated with THS remediation using ozone, providing insights into this technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Dicarboxylic acid emissions from a GDI engine equipped with a catalytic gasoline particulate filter

Dicarboxylic acids play an important role in atmospheric chemistry, yet their emissions from primary sources, such as internal combustion engines, has not been extensively studied. In this paper, KOH impregnated quartz filters were loaded with exhaust gases from a gasoline direct injection (GDI) engine equipped with a catalytic gasoline particulate filter (GPF). All filters were analyzed for carboxylic and dicarboxylic acids using a derivatized gas chromatography-mass spectroscopy method. Exhaust gas was sampled from pre-GPF and post-GPF locations to determine the performance of the GPF regarding acid conversion. Lean and stoichiometric engine modes were considered with non-oxygenated gasoline and 10% splash blended ethanol in gasoline (E10) to examine the impact of stoichiometry and fuel type. Acid emissions represented as much as 0.51% of total unburned hydrocarbon emissions for total monocarboxylic acids and as much as 0.40% for total dicarboxylic acids. Individual acid concentrations were as high as 38 mg/kg-fuel for monocarboxylic acids and as high as 29 mg/kg-fuel for dicarboxylic acids. Overall, the study found that fuel oxygenates had mixed impact on the acid emissions. Engine-out monocarboxylic acids were reduced when using the E10 fuel by approximately 30–45% for the stoichiometric condition and increased marginally for the lean condition. Dicarboxylic acid emissions were generally insensitive to ethanol content. However, the engine condition significantly affected the acid emissions. Lean operation produced a factor of two to an order of magnitude higher emissions rates of both monocarboxylic and dicarboxylic acids than the stoichiometric condition. The catalytic GPF eliminated between 80 and 92% of the acids emitted from the engine, allowing some acids to be emitted into the environment.

42 ENGINEERING↗

DOE OSTI2020

Clumped 13 CH 2 D and 12 CHD 2 compositions of methyl groups from wood and synthetic monomers: Methods, experimental and theoretical calibrations, and initial results

Methyl groups are found in numerous biogenic and synthetic materials including geologically preserved materials such as wood. The carbon and hydrogen isotope compositions of methyl groups are used as tracers in biogeochemical cycles, as paleothermometers, and to determine the hydrogen isotopic composition of ancient rain. Here we present analyses of resolved 13 C–D ( 13 CH 2 D) and D–D ( 12 CHD 2 ) clumped isotope compositions of methyl groups as new variables for the study of methyl groups in the present and past. We first present chemical methods to extract, purify, and derivatize methyl groups from methoxyl (R–O–CH 3 ) groups as CH 3 F and CH 3 Cl, and high-resolution mass spectrometric techniques to determine the clumped isotope compositions of these species. We achieve precisions for 13 C–D clumping of ±0.25‰ and D–D clumping of ±2.5‰. We anchor our clumped isotopic measurements to a thermodynamic reference frame by first calculating the theoretical temperature dependences of 13 C–D and D–D clumping in CH 3 Cl, then placing our measurements onto this reference frame through experimental internal isotopic equilibration of CH 3 Cl at 200 °C. Finally, we provide and analyze an initial dataset of clumped 13 C–D and D–D compositions of methyl groups from various commercial/synthetic monomers and environmental woods. We observe ranges in clumped isotope compositions of ~11‰ in 13 C–D and ~48‰ in D–D, and systematic differences within these ranges between methyl groups from commercial monomers and wood. Specifically, commercial clumped 13 C–D compositions are between 0 and 3‰, which correspond to apparent equilibrium temperatures between 170 °C and the infinite temperature limit. In contrast, the clumped 13 C–D compositions of wood methoxyl groups are distinctively high (9.50–11.25‰) and 3–6‰ higher than would be expected if formed in internal isotopic equilibrium at Earth-surface temperatures. Commercial/synthetic methyl and wood methoxyl clumped D–D compositions are also distinct: -5 to +13‰ in commercial monomers vs. -35 to -8‰ in wood—such negative values cannot result from formation in isotopic equilibrium and require kinetic processes to have occurred. Overall, these results indicate that wood methoxyl groups are formed out of isotopic equilibrium and that clumped isotope compositions of methyl groups may be useful tracers of methyl group sources and sinks in the environment. For instance, isotopic clumping in methyl groups may be useful for understanding controls on isotopic clumping in methane produced by methylotrophic methanogens.

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