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At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Strategic Lifetime Tuning of Visible-Light Absorbing Two-Coordinate Metal Complexes

This paper highlights how the singlet and triplet amide ligand centered ( 1,3 LC) and interligand charge transfer ( 1,3 ICT) states in (carbene)M(amide), M = Cu, Au (cMa) complexes influence the excited state properties when the triplet states are close in energy. To that end we prepared a set of five cMa complexes, in which the amide (i.e., 5H-benzo[b]carbazole, H-BnCz) was kept constant giving a 3 LC energy of ca. 2.15 eV. Four different carbene ligands were selected to develop M BnCz Carbene complexes which have energies for the ICT state that vary from being either markedly higher, lower, or close to the energy of the 3 LC state on the amide ligand. Steady-state and time-resolved spectroscopic studies show that the emission spectrum of the cMa complex mirrors the phosphorescence of the parent H-BnCz amide and has a luminescence decay lifetime in the millisecond regime when the lowest energy excited state is 3 LC. When the lowest energy states are 1,3 ICT in nature, the emission band is broad and featureless, giving a lifetime in the nanosecond regime. As the 3 LC and 1,3 ICT states have comparable energies, dynamic equilibrium between the states is observed with the luminescence consisting of a mixture of 3 LC and 1,3 ICT transitions. The measured lifetime of this equilibrating system is between 45 and 350 μs depending on the solvent, for both copper- and gold-based cMa complexes. Furthermore, these complexes demonstrate the ability to “park” the excited state population in the 3 LC state, allowing it to act as a reservoir for thermally activated emission, while still maintaining a very rapid equilibrium between LC and ICT states.

14 SOLAR ENERGY↗
DOE OSTI2019

A strategy to improve the performance of cerium(iii) photocatalysts

A structural modification strategy to improve the photocatalytic performance of a series of cerium(III) bis(guanidinate) mono(amide) molecular luminophores was demonstrated. Reducing the steric bulkiness of the amide ligand gave rise to two categories of complexes with distinct photophysical and photochemical properties. A structural parameter, the amide cone angle (θ), was applied to differentiate the two categories. Complexes with smaller cone angles (θ < 156°, category B) exhibited more reducing potentials and faster electron-transfer rates than those of complexes with larger cone angles (θ > 173°, category A). And only complexes in the category B could achieve the photocatalytic phenylation of an aryl bromide. These results demonstrated that reducing the steric bulkiness of the amide ligand improved the performance of cerium(III) bis(guanidinate) mono(amide) photocatalysts in a systematic manner.

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

Synthesis and anticancer effects of conjugates of doxorubicin and unsaturated fatty acids (LNA and DHA)

Doxorubicin (DOX) is a leading cytostatic drug with many adverse effects in use. We are still looking for methods that will allow us to preserve the therapeutic effect against the tumor cells and reduce the toxicity to the normal cells. In our work, we obtained amide derivatives of DOX by reaction of the amino group with α-linolenic (LNA) and docosahexaenoic (DHA) acids (2, 3), as well as double-substituted derivatives via amide and ester linkages (4, 5). The structures of the compounds were confirmed by Proton Nuclear Magnetic Resonance (1H NMR), Carbon-13 Nuclear Magnetic Resonance (13C NMR), and High Resolution Mass Spectrometry (HRMS) analyses. For all compounds 3-(4,5-dimethylthiazolyl-2)-2,5-diphenyltetrazolium bromide (MTT) assay was used to determine the cytotoxic effect on human cancer cell lines (SW480, SW620, and PC3) and Chinese hamster lung fibroblasts (V79) that were used as a control. The cytotoxic activity was established by calculation of the inhibitory concentration IC{sub 50}. In addition, a cytotoxic capacity against tumor cells for tested compounds was expressed as a selectivity factor (selectivity index, SI). Lactate dehydrogenase (LDH) assay was performed for all compounds to assess the level of cell damage. To explain the basic mechanism of cell death induction the Annexin V-FITC/IP flow cytometry analysis was investigated. We found that all studied conjugates exhibit lower cytotoxicity but higher selectivity than DOX. Among the all derivatives, the conjugates formed by the amide and ester linkages (4, 5) were found to be more promising compared with conjugates (2, 3) formed only by the amide linkage. They show high cytotoxicity toward the tumor cell lines and moderate cytotoxicity towards the normal cell line.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2024

Structural Effects on Solubility and Crystallinity in Polyamide Ionomers

Although polyamides have been an industrial staple for decades, their solubility and processability remain limited due to the strong hydrogen bonding between amide groups. Here, we report a family of polyamides in which aryl rings, alkyl spacers, sulfonate groups, and amide linkages are regularly spaced along the polymer backbone, allowing us to probe the structural elements that affect processability. We accessed these polymers through a synthetic route based on an expanded diamine monomer and characterized them through a range of physical and spectroscopic techniques. Our results show that the combination of sulfonate groups with increased amide content results in highly soluble polymers, which can dissolve in polar solvents such as water, methanol, and N,N-dimethylformamide. Infrared spectroscopy on the solid polymers shows that the aliphatic amides engage in hydrogen bonding with the sulfonate groups, thus inhibiting ion aggregation, crystallization, and microphase separation. These findings expand the avenue to sulfonate-containing polyamide chemistry and provide design rules for the synthesis of more processable ionic polyamides.

amides↗
DOE OSTI2016

Chemical Conversion of Linkages in Covalent Organic Frameworks

The imine linkages of two layered, porous covalent organic frameworks (COFs), TPB-TP-COF ([C 6 H 3 (C 6 H 4 N) 3 ] 2 [C 6 H 4 (CH) 2 ] 3 , 1) and 4PE-1P-COF ([C 2 (C 6 H 4 N) 4 ][C 6 H 4 (CH) 2 ] 2 , 2), have been transformed into amide linkages to make the respective isostructural amide COFs 1' and 2' by direct oxidation with retention of crystallinity and permanent porosity. Remarkably, the oxidation of both imine COFs is complete, as assessed by FT-IR and 13 C CP-MAS NMR spectroscopy and demonstrates (a) the first chemical conversion of a COF linkage and (b) how the usual “crystallization problem” encountered in COF chemistry can be bypassed to access COFs, such as these amides, that are typically thought to be difficult to obtain by the usual de novo methods. The amide COFs show improved chemical stability relative to their imine progenitors.

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

Electrochemical Oxidation of Organic Molecules at Lower Overpotential: Accessing Broader Functional Group Compatibility with Electron-Proton Transfer Mediators

CONSPECTUS: Electrochemical organic oxidation reactions are highly appealing because protons are often effective terminal electron acceptors, thereby avoiding undesirable stoichiometric oxidants. These reactions are often plagued by high overpotentials, however, that greatly limit their utility. Single-electron transfer (SET) from organic molecules generates high energy radical-cations. Formation of such intermediates often requires electrode potentials far above the thermodynamic potentials of the reaction and frequently causes decomposition and/or side reactions of ancillary functional groups. In this Account, we show how electrocatalytic electron-proton transfer mediators (EPTMs) address this challenge. EPTMs bypass the formation of radical-cation intermediates by supporting mechanisms that operate at electrode potentials much lower (=1 V) than analogous direct electrolysis reactions. The stable aminoxyl radical TEMPO (2,2,6,6-tetramethylpiperidine N-oxyl) is an effective mediator for electrochemical alcohol oxidation, and we have employed such processes for applications ranging from pharmaceutical synthesis to biomass conversion. A complementary electrochemical alcohol oxidation method employs a cooperative Cu/TEMPO mediator system that operates at 0.5 V lower electrode potential than the TEMPO-only mediated process. This difference, which arises from a different catalytic mechanism, rationalizes the broad functional group tolerance of Cu/TEMPO-based aerobic alcohol oxidation catalysts. Aminoxyl mediators address long-standing challenges in the "Shono oxidation", an important method for a-C–H oxidation of tertiary amides and carbamates. Shono oxidations are initiated by a high-potential SET step that limits their utility. Aminoxyl-mediated Shono-type oxidations have been developed that operate at much lower potentials and tolerate diverse functional groups. Analogous reactivity underlies a-C–H cyanation of secondary cyclic amines, a new method that enables efficient diversification of piperidine-based pharmaceutical building blocks and preparation of non-natural amino acids. Electrochemical oxidations of benzylic C–H bonds are commonly initiated by SET to generate radical cations, but such methods are again plagued by large overpotentials. Mediated electrolysis methods that promote hydrogen-atom-transfer (HAT) from benzylic C–H bonds to Fe-oxo species and phthalimide N-oxyl (PINO) support C–H oxygenation, iodination, and oxidative-coupling reactions. A complementary method merges photochemistry with electrochemistry to achieve amidation of C(sp3)–H bonds. This unique process operates at much lower overpotentials compatible with diverse functional groups. These results have broad implications for organic electrochemistry, highlighting the importance of "overpotential" considerations and the prospects for expanding synthetic utility by using mediators to bypass high-energy outer-sphere electron-transfer mechanisms. Principles demonstrated here for oxidation are equally relevant to electrochemical reductions.

Wang, Fei↗
DOE OSTI2022

Hydrogen Atom Abstraction from an Os II (NH 3 ) 2 Complex Generates an Os IV (NH 2 ) 2 Complex: Experimental and Computational Analysis of the N–H Bond Dissociation Free Energies and Reactivity

We report double hydrogen atom abstraction from (TMP)Os II (NH 3 ) 2 (TMP = tetramesitylporphyrin) with phenoxyl or nitroxyl radicals leads to (TMP)Os IV (NH 2 ) 2 . This unusual bis(amide) complex is diamagnetic and displays an N-H resonance at 12.0 ppm in its 1 H NMR spectrum. 1 H- 15 N correlation experiments identified a 15 N NMR spectroscopic resonance at –267 ppm. Experimental reactivity studies and density functional theory calculations support relatively weak N-H bonds of 73.3 kcal/mol for (TMP)Os II (NH 3 ) 2 and 74.2 kcal/mol for (TMP)Os III (NH 3 )(NH 2 ). Cyclic voltammetry experiments provide an estimate of the pK a of [(TMP)Os III (NH 3 ) 2 ] + . In the presence of Barton’s base, a current enhancement is observed at the Os(III/II) couple, consistent with an ECE event. Spectroscopic experiments confirmed (TMP)Os IV (NH 2 ) 2 as the product of bulk electrolysis. Double hydrogen atom abstraction is influenced by π donation from the amides of (TMP)Os IV (NH 2 ) 2 into the d orbitals of the Os center, favoring the formation of (TMP)Os IV (NH 2 ) 2 over N-N coupling. This π donation leads to a Jahn-Teller distortion that splits the energy levels of the d xz and d yz orbitals of Os, results in a low spin electron configuration, and leads to minimal aminyl character on the N atoms, rendering (TMP)Os IV (NH 2 ) 2 unreactive towards amide-amide coupling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Probing Solvation-Induced Structural Changes in Conformationally Flexible Peptides: IR Spectroscopy of Gly 3 H + •(H 2 O)

IR predissociation spectroscopy of the Gly 3 H + (H 2 O) complex formed inside of a cryogenic ion trap reveals how the flexible model peptide structurally responds to solvation by a single water molecule. The resulting one-laser spectrum is quite congested, and the spectral analyses were assisted by both H 2 O/D 2 O substitution and IR–IR double resonance spectroscopy, revealing the presence of two contributing isomers and extensive anharmonic features. Comparisons to structures found via a systematic computational search identified the geometries of these two isomers. The major isomer, with all trans amide bonds and protonation on the terminal amine, represents ~90% of the overall population. It noticeably differs from the unsolvated Gly 3 H + , which exists in two isomeric forms: one with a cis amide bond and the other with protonation on an amide C=O. These results indicate that interactions with just one water molecule can induce significant structural changes, i.e., cis–trans amide bond rotation and proton migration, even as the clustering occurs within an 80 K cryogenic ion trap. In conclusion, calculations of the isomerization pathways further reveal that the binding energy of the water molecule provides sufficient internal energy to overcome the barriers for the observed structural changes, and the minor solvation isomer results from a small fraction of the ions being kinetically trapped along one of the pathways.

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

Decoding the Desorption Mechanism of 2LiH:1Mg(NH2)2 Using Metal Borohydrides

The complex metal hydride 2LiH:1Mg­(NH2)2 has emerged as a promising material for stationary hydrogen storage applications, such as seasonal storage or energy backup systems, due to its high volumetric and gravimetric capacities and robust reversibility. However, its widespread adoption is hindered by sluggish reaction rates, performance degradation upon cycling, and improper end-use cases. To address these problems and better understand the desorption pathway, we used metal borohydrides (MBH4; M = Li–Cs) as chemical probes. A thorough analysis of the bulk behavior of all six materials, including hydrogen cycling experiments, X-ray absorption spectroscopy, FTIR, pXRD, solid-state NMR, and ab initio DFT simulations, shows that the borohydride additives decrease the activation energy of hydrogen release by about 20 kJ/mol for MBH4@2:1 materials versus pristine. Furthermore, more surface-sensitive studies show that the amide-to-imide desorption pathway in these materials, while essentially complete in the bulk, is incomplete in the near-surface region, suggesting an “inverse core–shell” desorption mechanism for amide dehydrogenation to imide. The kinetic enhancements produced by MBH4 additives (M = K, Rb, and Cs) are attributed to the destabilization of the amide N–H bond and interaction with the LiH/Mg­(NH2)2 interface to promote H–H bond formation. An inverse core-shell mechanism is also operative in the hydrogen desorption for the 2LiH:1LiNH2 system, suggesting this may be a general feature of amides. Given the fast dehydrogenation rate and large gravimetric capacity, these materials satisfy these requirements for telecom backups and seasonal microgrid storage applications.

Absorption↗
DOE OSTI2014

The Radiation Chemistry of CMPO: Part 2. Alpha Radiolysis

Here, Octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) dissolved in dodecane was subjected to α-irradiation using a He-ion beam, 244 Cm isotopic α-rays, and He and Li ions created by the n,α reaction of 10 B in a nuclear reactor. Post-irradiation samples were analyzed for the radiolytically-induced decrease in CMPO concentration, the appearance of degradation products, and their Am solvent extraction distribution ratios. The –G CMPO -value for the radiolytic degradation of CMPO was found to be very low compared to values previously reported for γ-irradiation. Additionally, isotopic irradiation to absorbed α-doses as high as 600 kGy in aerated solution had no effect on Am solvent extraction or stripping. The main CMPO radiolysis products identified in He-ion beam irradiated samples by ESI-MS include amides, an acidic amide, and amines produced by bond rupture on either side of the CMPO carbonyl group. Deaerated samples irradiated using the reactor in the absence of an aqueous phase, or with a dilute nitric acid aqueous phase showed small but measurable decreases in CMPO concentration with increasing absorbed doses. Higher concentrations of nitric acid resulted in lower decomposition rates for the CMPO. The radio-protection by dissolved oxygen and nitric acid previously found for γ-irradiated CMPO also occurs for α-irradiation. This suggests that similar free-radical mechanisms operate in the high-LET system, but with lower degradation yields due to the lower overall radical concentrations produced.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
NASA NTRS1997

Diamines Containing Pendent Phenylethynyl Groups

Controlled molecular weight imide oligomers and co-oligomers containing pendent phenylethynyl groups (PEPIs) and endcapped with nonreactive or phenylethynyl groups have been prepared by the cyclodehydration of the precursor amide acid oligomers or co-oligomers containing pendent phenylethynyl groups and endcapped with nonreactive or phenylethynyl groups. The amine terminated amide acid oligomers or co-oligomers are prepared from the reaction of dianhydride(s) with an excess of diamine(s) and diamine containing pendent phenylethynyl groups and subsequently endcapped with a phenylethynyl phthalic anhydride or monofunctional anhydride. The anhydride terminated amide acid oligomers and co-oligomers are prepared from the reaction of diamine(s) and diamine containing pendent phenylethynyl group(s) with an excess of dianhydride(s) and subsequently endcapped with a phenylethynyl amine or monofunctional amine. The polymerizations are carried out in polar aprotic solvents such as and N,N-dimethylacetamide under nitrogen at room temperature. The amide acid oligomers or co-oligomers are subsequently cyclodehydrated either thermally or chemically to the corresponding imide oligomers. The polymers and copolymers prepared from these materials exhibit a unique and unexpected combination of properties that includes higher glass transition temperatures after curing and higher retention of neat resin, adhesive and carbon fiber reinforced mechanical properties at temperatures up to 204 C under wet conditions without sacrificing melt flow behavior and processability as compared to similar materials. These materials are useful as adhesives, coatings, films, moldings, and composite matrices.

Connell, John W.↗
NASA NTRS2005

Reactive Additives for Phenylethynyl-Containing Resins

Phenylethynyl-containing reactive additive (PERA) compounds and mixtures have been found to be useful for improving the processability of oligomers, polymers, co-oligomers, and copolymers that contain phenylethynyl groups. The additives can be incorporated in different forms: A solution of an amide acid or an imide of a PERA can be added to a solution of phenylethynyl-containing oligomer, polymer, co-oligomer, or copolymer; or An imide powder of a PERA can be mixed with a dry powder of a phenylethynyl-containing oligomer, polymer, co-oligomer, or copolymer. The effect of a given PERA on the processability and other properties of the resin system depends on whether the PERA is used in the amide acid or an imide form. With proper formulation, the PERA reduces the melt viscosity of the resin and thereby reduces the processing pressures needed to form the adhesive bonds, consolidate filled or unfilled moldings, or fabricate fiber-reinforced composite laminates. During thermal cure, a PERA reacts with itself as well as with the phenylethynyl-containing host resin and thereby becomes chemically incorporated into the resin system. The effects of the PERA on mechanical properties, relative to those of the host resin, depend on the amount of PERA used. Typically, the incorporation of the PERA results in (1) increases in the glass-transition temperature (Tg), modulus of elasticity, and parameters that characterize behavior under compression, and (2) greater retention of the aforementioned mechanical properties at elevated temperatures without (3) significant reduction of toughness or damage tolerance. Of the formulations tested thus far, the ones found to yield the best overall results were those for which the host resin was the amide acid form of a phenylethynyl-terminated imide (PETI) co-oligomer having a molecular weight of 5,000 g/mole [hence, designated PETI-5] and a PERA denoted as PERA-1. PETI-5 was made from 3,3',4'4'-biphenyltetracarboxylic dianhydride, 3,4'-oxydianiline (3,4'-ODA), 1,3-bis(3-aminophenoxy) benzene (1,3-APB), and 4-phenylethynylphthalic anhydride (PEPA). PERA-1 was made from 3,5-diamino- 4.-phenylethynylbenzophenon and equimolar amounts of phthalic anhydride and PEPA. To make PERA-1 in the imide form, the aforementioned ingredients were processed by refluxing in glacial acetic acid. To make the amide form of PERA-1, the ingredients were reacted in N-methyl-2-pyrrolidinone (NMP) under nitrogen at a temperature of 23 C (see figure). On the basis of the processability and other properties, a blend comprising 20 weight percent of PERA-1 and 80 weight percent PETI-5 was selected for further evaluation. Relative to neat PETI-5, the blend exhibited an increase in Tg; improved processability; and comparable values of shear strength in adhesion to titanium panels, open-hole compressive properties, compression properties after impact, and resistance to microcracking.

Connell, John W.↗
DOE OSTI2023

Quantitative Separation of Unknown Organic–Metal Complexes by Liquid Chromatography–Inductively Coupled Plasma-Mass Spectrometry

Dissolved organic matter (DOM) is widely recognized to control the solubility and reactivity of trace metals in the environment. However, the mechanisms that govern metal-DOM complexation remain elusive, primarily due to the analytical challenge of fractionating and quantifying metal–organic species within the complex mixture of organic compounds that comprise DOM. Here, we describe a quantitative method for fractionation and element-specific detection of organic–metal complexes using liquid chromatography with online inductively coupled plasma mass spectrometry (LC–ICP-MS). The method implements a post-column compensation gradient to stabilize ICP–MS elemental response across the LC solvent gradient, thereby overcoming a major barrier to achieving quantitative accuracy with LC–ICP-MS. With external calibration and internal standard correction, the method yields concentrations of organic–metal complexes that were consistently within 6% of their true values, regardless of the complex’s elution time. We used the method to evaluate the effects of four stationary phases (C18, phenyl, amide, and pentafluoroylphenyl propyl) on the recovery and separation of environmentally relevant trace metals (Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb) in Suwannee River Fulvic Acid and Suwannee River Natural Organic Matter. The C18, amide, and phenyl phases generally yielded optimal metal recoveries (>75% for all metals except Pb), with the phenyl phase separating polar species to a greater extent than C18 or amide. We also fractionated organic-bound Fe, Cu, and Ni in oxidized and reduced soils, revealing divergent metal-DOM speciation across soil redox environments. Finally, by enabling quantitative fractionation of DOM-bound metals, our method offers a means for advancing a mechanistic understanding of metal–organic complexation throughout the environment.

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

Buried Hydrogen Bond Interactions Contribute to the High Potency of Complement Factor D Inhibitors

Aberrant activation of the complement system is associated with diseases, including paroxysmal nocturnal hemoglobinuria and age-related macular degeneration. Complement factor D is the rate-limiting enzyme for activating the alternative pathway in the complement system. Recent development led to a class of potent amide containing pyrrolidine derived factor D inhibitors. Here, we used biochemical enzymatic and biolayer interferometry assays to demonstrate that the amide group improves the inhibitor potency by more than 80-fold. Our crystal structures revealed buried hydrogen bond interactions are important. Molecular orbital analysis from quantum chemistry calculations dissects the chemical groups participating in these interactions. Free energy calculation supports the differential contributions of the amide group to the binding affinities of these inhibitors. Cell-based hemolysis assay confirmed these compounds inhibit factor D mediated complement activation via the alternative pathway. Our study highlights the important interactions contributing to the high potency of factor D inhibitors reported recently.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Microprobing the Molecular Spatial Distribution and Structural Architecture of Feed-type Sorghum Seed Tissue (Sorghum Bicolor L.) using the Synchrotron Radiation Infrared Microspectroscopy Technique

Sorghum seed (Sorghum bicolor L.) has unique degradation and fermentation behaviours compared with other cereal grains such as wheat, barley and corn. This may be related to its cell and cell-wall architecture. The advanced synchrotron radiation infrared microspectroscopy (SR-IMS) technique enables the study of cell or living cell biochemistry within cellular dimensions. The objective of this study was to use the SR-IMS imaging technique to microprobe molecular spatial distribution and cell architecture of the sorghum seed tissue comprehensively. High-density mapping was carried out using SR-IMS on beamline U2B at the National Synchrotron Light Source (Brookhaven National Laboratory, NY, USA). Molecular images were systematically recorded from the outside to the inside of the seed tissue under various chemical functional groups and their ratios [peaks at {approx}1725 (carbonyl C=O ester), 1650 (amide I), 1657 (protein secondary structure {alpha}-helix), 1628 (protein secondary structure {beta}-sheet), 1550 (amide II), 1515 (aromatic compounds of lignin), 1428, 1371, 1245 (cellulosic compounds in plant seed tissue), 1025 (non-structural CHO, starch granules), 1246 (cellulosic material), 1160 (CHO), 1150 (CHO), 1080 (CHO), 930 (CHO), 860 (CHO), 3350 (OH and NH stretching), 2960 (CH{sub 3} anti-symmetric), 2929 (CH{sub 2} anti-symmetric), 2877 (CH{sub 3} symmetric) and 2848 cm{sup -1} (CH{sub 2} asymmetric)]. The relative protein secondary structure {alpha}-helix to {beta}-sheet ratio image, protein amide I to starch granule ratio image, and anti-symmetric CH{sub 3} to CH{sub 2} ratio image were also investigated within the intact sorghum seed tissue. The results showed unique cell architecture, and the molecular spatial distribution and intensity in the sorghum seed tissue (which were analyzed through microprobe molecular imaging) were generated using SR-IMS. This imaging technique and methodology has high potential and could be used for scientists to develop specific cereal grain varieties with targeted food and feed quality, and can also be used to monitor the degree of grain maturity, grain damage, the fate of organic contaminants and the effect of chemical treatment on plant and grain seeds.

09 BIOMASS FUELS↗
DOE OSTI2015

Designer synthetic media for studying microbial-catalyzed biofuel production

Background: The fermentation inhibition of yeast or bacteria by lignocellulose-derived degradation products, during hexose/pentose co-fermentation, is a major bottleneck for cost-effective lignocellulosic biorefineries. To engineer microbial strains for improved performance, it is critical to understand the mechanisms of inhibition that affect fermentative organisms in the presence of major components of a lignocellulosic hydrolysate. The development of a synthetic lignocellulosic hydrolysate (SH) media with a composition similar to the actual biomass hydrolysate will be an important advancement to facilitate these studies. In this work, we characterized the nutrients and plant-derived decomposition products present in AFEX™ pretreated corn stover hydrolysate (ACH). The SH was formulated based on the ACH composition and was further used to evaluate the inhibitory effects of various families of decomposition products during Saccharomyces cerevisiae 424A (LNH-ST) fermentation. Results: The ACH contained high levels of nitrogenous compounds, notably amides, pyrazines, and imidazoles. In contrast, a relatively low content of furans and aromatic and aliphatic acids were found in the ACH. Though most of the families of decomposition products were inhibitory to xylose fermentation, due to their abundance, the nitrogenous compounds showed the most inhibition. From these compounds, amides (products of the ammonolysis reaction) contributed the most to the reduction of the fermentation performance. However, this result is associated to a concentration effect, as the corresponding carboxylic acids (products of hydrolysis) promoted greater inhibition when present at the same molar concentration as the amides. Due to its complexity, the formulated SH did not perfectly match the fermentation profile of the actual hydrolysate, especially the growth curve. However, the SH formulation was effective for studying the inhibitory effect of various compounds on yeast fermentation. Conclusions: The formulation of SHs is an important advancement for future multi-omics studies and for better understanding the mechanisms of fermentation inhibition in lignocellulosic hydrolysates. The SH formulated in this work was instrumental for defining the most important inhibitors in the ACH. Major AFEX decomposition products are less inhibitory to yeast fermentation than the products of dilute acid or steam explosion pretreatments; thus, ACH is readily fermentable by yeast without any detoxification.

09 BIOMASS FUELS↗
DOE OSTI2023

Stretchable and Self‐Healable Semiconductive Composites Based on Hydrogen Bonding Cross‐linked Elastomeric Matrix

Abstract Semiconductors with both high stretchability and self‐healing capability are highly desirable for various wearable devices. Much progress has been achieved in designing highly stretchable semiconductive polymers or composites. The demonstration of self‐healable semiconductive composite is still rare. Here, an extremely soft, highly stretchable, and self‐healable hydrogen bonding cross‐linked elastomer, amide functionalized‐polyisobutylene (PIB‐amide) is developed, to enable a self‐healable semiconductive composite through compounding with a high‐performance conjugated diketopyrrolopyrrole (DPP‐T) polymer. The composite, consisting of 20% DPP‐T and 80% PIB‐amide, shows record high crack‐onset strain (COS ≈1500%), extremely low elastic modulus (E≈1.6 MPa), and unique ability to spontaneously self‐heal atroom temperature within 5 min. Unlike previous works, these unique composite materials also show strain‐independent charge mobility. An in‐depth morphological study based on multi‐model techniques indicate that all composites show blending ratio‐ and stretching‐independent fibril‐like aggregation due to the strong hydrogen bond in elastomer to enable the unique stable charge mobility. This study provides a new direction to develop highly healable and electronically stable semiconductive composite and will enable new applications of stretchable electronics.

Chemistry↗