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At least 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Effects of CELF Pretreatment Severity on Lignin Structure and the Lignin-Based Polyurethane Properties

Conversion of technical lignin into performance biopolymers such as polyurethane offers environmental and economic advantages when combined with production of biofuels from biomass sugars, presenting significant interest toward studying the role of pretreatment on lignin structure and functionality. Co-solvent enhanced lignocellulosic fractionation (CELF) pretreatment, employing acidic aqueous tetrahydrofuran (THF) mixtures, was developed to effectively break down the lignin-carbohydrate matrix and promote extraction of lignin from lignocellulosic biomass with desirable purity and yield. In this study, we report the effects of CELF pretreatment reaction severity on the molecular structure of CELF-extracted lignin and its impact toward the mechanical properties of the resulting lignin-based polyurethanes. Reaction temperature was found to play the most significant role, compared to reaction time and acidity, in manipulating structural features such as molecular weight, functionality and intra-polymer structure. At the severe reaction conditions at 180°C, the order of reactivity for primary lignin interlinkages characterized by semiquantitative HSQC NMR analysis were found to be β-ether > phenylcoumaran (β−5′) > resinol (β−β′) facilitating a high degree of depolymerization and yielding a high frequency of free phenolics and reduced aliphatic hydroxyl groups. All side-chain interlinkages were depleted converting guaiacyl subunits into condensed forms, while still retaining uncondensed syringyl subunits. Under the mild 150°C temperature reaction, CELF lignin had higher molecular weight and retained more β-ether interlinkages. The results from CELF lignin-based polyurethane synthesis indicated that the tensile properties depended on the miscibility of CELF lignin with other components and low molecular weight cuts improved the dispersion of lignin in the polyurethane network. Pre-mixing of CELF with poly(ethylene glycol) (PEG) reduced the brittleness and improved the ductility of the CELF lignin-PEG polyurethanes.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS2020

Interpreting Exo-Planetary Atmospheres with the Next Generation Space-Based Telescope

We will soon have the technological capability to measure the atmospheric composition of temperate Earth-sized planets orbiting nearby stars. Interpreting these atmospheric signals poses a new challenge to planetary science. In contrast to jovian-like atmospheres, whose bulk compositions consist of hydrogen and helium, terrestrial planet atmospheres are likely comprised of high mean molecular weight secondary atmospheres, which have gone through a high degree of evolution. In order to understand the processes which affect a planetary atmosphere, I use early Mars as a case study. I leverage a combination of one-dimensional climate, photochemical and energy balance models in order to create one self-consistent model that closely matches currently available climate data. However, unlike in-situ observations from our own solar system, remote sensing techniques need to be developed and understood in order to accurately characterize exo-atmospheres. I describe the models used to create synthetic transit transmission observations, which includes models of transit spectroscopy and instrumental noise. Using these, I lay the framework for an information content-based approach to optimize our observations and maximize the retrievable information from exo-atmospheres. First I test the method on observing strategies of the well-studied, low-mean-molecular weight atmospheres of warm-Neptunes and hot Jupiters. Upon verifying the methodology, I finally address optimal observing strategies for temperate, high-mean-molecular weight atmospheres (Earths/super-Earths).

Batalha, Natasha↗
NASA NTRS2000

Cold Spots in the Martian Polar Regions: Evidence of Carbon Dioxide Depletion?

Regions of very low, rapidly varying brightness temperatures have been observed near the martian winter poles by several spacecraft. One possibility is that the CO2 condensation temperature is lowered by depletion of CO2 in the air at the surface. We estimate the rate at which this low-molecular-weight air would disperse into the high-molecular-weight air above and show that it is generally faster than the rate of supply. This dispersal could be prevented if there is a strong temperature inversion (warm air above colder air) near the surface. Without an inversion, the entire atmospheric column could become depleted. However, depleted columns take a long time to form, and they are inconsistent with the rapid fluctuations in the cold spot locations and temperatures. Because low-altitude temperature inversions cannot be ruled out by existing observations, CO2 depletion is still a viable explanation for the martian cold spots.

Weiss, Benjamin P.↗
NASA NTRS1992

Availability of the B beta(15-21) epitope on cross-linked human fibrin and its plasmic degradation products

The binding of radiolabeled monoclonal antifibrin antibody 59D8 (specific for fibrin but not fibrinogen) to a series of degraded fibrin clots showed that the availability of the B beta(15-21) epitope (against which 59D8 had been raised) was inversely proportional to the extent of clot lysis. Examination of digest supernatants revealed that the B beta(15-21) epitope was released from clots as a high molecular weight degradation product in the presence of calcium ions but that the generation of low molecular weight peptides occurred in the absence of calcium ions. To address the question of epitope accessibility, we compared levels of fibrin clot binding among four radioactively labeled antibodies: antifibrin monoclonal antibody 59D8, two antifibrinogen monoclonal antibodies that cross-reacted with fibrin, and an affinity-purified polyclonal antifibrinogen antibody. We expected that the antifibrinogen antibodies would show enhanced binding to clots in comparison with the antifibrin antibody. However, the epitope accessibility experiments showed that all four antibody preparations bound fibrin clots at comparable levels. Taken together, these studies demonstrated that one fibrin-specific epitope, B beta(15-21), remains available on clots as they undergo degradation by plasmin and, importantly, that the epitope is not solubilized at a rate faster than the rate at which the clot is itself solubilized. The availability of the B beta(15-21) epitope during the course of plasminolysis assures the potential utility of antifibrin antibodies such as 59D8 for detecting thrombi and targeting plasminogen activators.

NASA Discipline Regulatory Physiology↗
DOE OSTI2020

Polymer Retention Evaluation in a Heavy Oil Sand for a Polymer Flooding Application on Alaska’s North Slope

For a polymer flooding field trial in a heavy oil reservoir on Alaska’s North Slope, polymer retention is a key parameter. Because of the economic impact of retention, this parameter was extensively studied using field core material and conditions. Several important findings were noted. Polymer retention based on effluent viscosity measurements can be overestimated unless the correct (non-linear) relation between polymer concentration and viscosity is used. Polymer degradation (either mechanical or oxidative) can also lead viscosity-based measurements to overestimate retention. Inaccessible pore volume (IAPV) can be overestimated if insufficient brine is flushed through the sand between polymer banks. Around 100 pore volumes (PV) of brine may be needed to displace mobile polymer to approach a true residual resistance factor and properly measure IAPV. Even for a sand pack with kwsor = 20 mD, IAPV was zero for HPAM with molecular weight (Mw) of 18 million g/mol. Fine-grain particles (<20 μm) strongly impacted polymer retention values. Native NB#1 sand with a significant component of particles <20 μm exhibited 290 μg/g, while the same sand exhibited 28 μg/g after these small particles were removed. Polymer retention did not necessarily correlate with mineral composition. The NB#1, NB#3, and OA sands had similar elemental and clay compositions, but the NB#1 sand exhibited ~10 times higher retention than the NB#3 sand. Polymer retention did not necessarily correlate with permeability. NB#1 sand exhibited much higher retention than OA sand, even though NB#1 sand was twice as permeable as OA sand. No evidence of chromatographic separation of HPAM molecular weights was found in our experiments. Although retention tended to be greater without a residual oil saturation (than at Sor), the effect was not strong. Aging a core (with high oil saturation) at 60°C reduced HPAM retention by a factor of two. As expected, under similar conditions, polymer retention was greater for a higher Mw HPAM (18 million g/mol) than for a lower Mw HPAM (10-12 million g/mol). In many cases with high polymer retention values (e.g., 240 μg/g), polymer arrival at the end of the core was relatively quick, but achieving the injected concentration occurred gradually over many pore volumes. This effect was not due chromatographic separation of polymer molecular weights. Results from modeling of this behavior was consistent with concentrationdependent polymer retention. The form assumed for the retention function in a simulator can have an important impact on the timing and magnitude of the oil response from a polymer flood. Field-based observations can underestimate polymer retention, depending on when the tracer and polymer concentrations were measured and the assumptions made about reservoir heterogeneity.

Wang, Dongmei↗
DOE OSTI2022

A Heterogeneous Palladium Catalyst for the Polymerization of Olefins Prepared by Halide Abstraction Using Surface R 3 Si + Species

Abstract The silylium‐like surface species [ i Pr 3 Si][(R F O) 3 Al−OSi≡)] activates (N^N)Pd(CH 3 )Cl (N^N=Ar−N=CMeMeC=N−Ar, Ar=2,6‐bis(diphenylmethyl)‐4‐methylbenzene) by chloride ion abstraction to form [(N^N)Pd−CH 3 ][(R F O) 3 Al−OSi≡)] ( 1 ). A combination of FTIR, solid‐state NMR spectroscopy, and reactions with CO or vinyl chloride establish that 1 shows similar reactivity patterns as (N^N)Pd(CH 3 )Cl activated with Na[B(Ar F ) 4 ]. Multinuclear 13 C{ 27 Al} RESPDOR and 1 H{ 19 F} S‐REDOR experiments are consistent with a weakly coordinated ion‐pair between (N^N)Pd−CH 3 + and [(R F O) 3 Al−OSi≡)]. 1 catalyzes the polymerization of ethylene with similar activities as [(N^N)Pd−CH 3 ] + in solution and incorporates up to 0.4 % methyl acrylate in copolymerization reactions. 1 produces polymers with significantly higher molecular weight than the solution catalyst, and generates the highest molecular weight polymers currently reported in copolymerization reactions of ethylene and methylacrylate.

Gao, Jiaxin↗
DOE OSTI2022

A Heterogeneous Palladium Catalyst for the Polymerization of Olefins Prepared by Halide Abstraction Using Surface R 3 Si + Species

The silylium-like surface species [ i Pr 3 Si][(R F O) 3 Al-OSi≡)] activates (N^N)Pd(CH 3 )Cl (N^N=Ar-N=CMeMeC=N-Ar, Ar=2,6-bis(diphenylmethyl)-4-methylbenzene) by chloride ion abstraction to form [(N^N)Pd-CH 3 ][(R F O) 3 Al-OSi≡)] ( 1 ). A combination of FTIR, solid-state NMR spectroscopy, and reactions with CO or vinyl chloride establish that 1 shows similar reactivity patterns as (N^N)Pd(CH 3 )Cl activated with Na[B(Ar F ) 4 ]. Multinuclear 13 C{ 27 Al} RESPDOR and 1 H{ 19 F} S-REDOR experiments are consistent with a weakly coordinated ion-pair between (N^N)Pd-CH 3 + and [(R F O) 3 Al-OSi≡)]. 1 catalyzes the polymerization of ethylene with similar activities as [(N^N)Pd-CH 3 ] + in solution and incorporates up to 0.4% methyl acrylate in copolymerization reactions. 1 produces polymers with significantly higher molecular weight than the solution catalyst, and generates the highest molecular weight polymers currently reported in copolymerization reactions of ethylene and methylacrylate.

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

The importance of nutrients for microbial priming in a bog rhizosphere

Wetlands host anaerobic microbes which convert organic carbon into methane (CH 4 ), a powerful greenhouse gas. Wetland plants can influence which carbon compounds are available for microbial processing by exuding freshly fixed carbon from their roots. Notably, exudation of carbon from plant roots can trigger microbial priming: the process of new carbon stimulating the microbial community into processing more soil carbon than they otherwise would have. This study utilized high resolution Fourier transform ion cyclotron mass spectrometry (FT-ICR-MS) analysis to probe the chemical composition of soil organic compounds from the rhizosphere of Carex aquatillis, a common wetland sedge, which is known to have stimulated microbial priming within a peat soil. The goal was to identify what types of molecules are created or lost during microbial priming in the wetland rhizosphere and thus advance mechanistic understanding of the process. FT-ICR-MS analysis demonstrated that more microbial transformations of carbon occurred among water-soluble compounds than among hydrophobic compounds, but that some hydrophobic compounds were processed as well. Crucially for understanding microbial priming, the root exudates triggered increased processing of high molecular weight molecules regardless of nutrient content but processed low molecular weight compounds only if they contained essential nutrients. Furthermore, the pattern of which molecules are processed and which are not is evidence for a selective priming effect in which some types of carbon compounds are used at an increased rate, while others are not.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1985

Polyimide analysis using diffuse reflectance-FTIR

The thermal imidization of a number of polyimide precursors in the form of powders, films, and prepregs was examined by an in situ diffuse reflectance-FTIR technique where infrared spectra were determined while the material was being heated. An analysis of these spectra revealed that, with the exception of one water soluble adhesive, each precursor developed an anhydride band around 1850 cm/cu during imidization. This band diminished in intensity during final stages of cure. Efforts were made to quantify the amount of anhydride in several samples. Evidence obtained could be interpreted to mean that poly(amic acid) resins undergo an initial reduction in molecular weight during imidization before recombining to achieve their ultimate molecular weights as polyimides. Several reports in the literature are cited to support this interpretation. This report serves both to document anhydride formation during imidization and to increase our fundamental understanding of how polyimides cure.

Young, P. R.↗
NASA NTRS1992

Polyimide processing additives

A process for preparing polyimides having enhanced melt flow properties is described. The process consists of heating a mixture of a high molecular weight poly-(amic acid) or polyimide with a low molecular weight amic acid or imide additive in the range of 0.05 to 15 percent by weight of additive. The polyimide powders so obtained show improved processability, as evidenced by lower melt viscosity by capillary rheometry. Likewise, films prepared from mixtures of polymers with additives show improved processability with earlier onset of stretching by TMA.

Fletcher, James C.↗
NASA NTRS1993

Polyimide processing additives

A process for preparing polyimides having enhanced melt flow properties is described. The process consists of heating a mixture of a high molecular weight poly-(amic acid) or polyimide with a low molecular weight amic acid or imide additive in the range of 0.05 to 15 percent by weight of the additive. The polyimide powders so obtained show improved processability, as evidenced by lower melt viscosity by capillary rheometry. Likewise, films prepared from mixtures of polymers with additives show improved processability with earlier onset of stretching by TMA.

Pratt, J. Richard↗
NASA NTRS1996

A Method for Characterizing Thermoset Polyimides

Thermoset polyimides have great potential for successfully meeting tough stress and temperature challenges in the advanced aircraft development program. However, studies of structure-property relationships in these materials have not been very successful so far. Positron lifetime spectroscopy (PLS) has been used to investigate free volumes and associated parameters in a series of variable, segmental molecular weight samples. The free volume correlates well with the molecular weight M(sub c), the cross-link density v, and the coefficient of thermal expansion (CTE) of these materials. Currently, no other techniques are available for direct measurement of these parameters, particularly for polymers in solid phase. Experimental results and their interpretations are presented.

Ranganathaiah, C.↗
NASA NTRS1966

Fully Deuterated Aliphatic Hydrocarbons Obtained From Iron Carbide Treated with DCl and D2O

According to Oparin, Mendeleev thought that the origin of petroleum was the result of the hydrolysis of iron carbides by superheated steam under pressure from the deep interior of the Earth through geological formations where the metal carbides exist. As early as 1877, Mendeleev described the reaction leading to the synthesis of hydrocarbons according to the general equation 3Fe(sub m)C(sub n) + mH2O yields mFe3O4 + C(sub 3n)H(sub 8m). Other experimental studies on the production of hydrocarbons from cast iron have been reported. Because of the possibility that hydrocarbons may have been trapped within the carbon matrix of the cast iron, which usually has a high content of carbon, we have studied the reaction of pure iron carbide with deuterium chloride and deuterated water. This was done in order to distinguish any newly formed deuterated hydrocarbons from any possible impurities of trapped hydrocarbons. The experiments were carried out by simply allowing iron carbide to react with concentrated deuterium chloride in D2O. The volatile hydrocarbon fraction examined by gas chromatography-mass spectrometry (GC/MS), using a Finnigan 1020/OWA instrument. contained low molecular weight hydrocarbons in a range C3 to C7. Lower molecular weight hydrocarbons were not detected by GC/MS because the MS scanning mode was preset above mass 40 to exclude components of air. The identified hydrocarbons are similar to those obtained under prebiotic conditions using high frequency discharge. The hydrocarbons found in common were propane, butane, pentane, 3-methylpentane, hexane, and heptane. The percent yields decline with increasing carbon number (propane 11%, n-heptane 1%). Similar results have been obtained by the direct treatment of metal carbides by pulse laser vaporization mass spectrometry. These results show that the hydrolysis of iron carbides may have been a significant source of hydrocarbons on the primitive Earth. There appears to be a predominance of straight chain isomers, which may have been important in the prebiotic synthesis of membrane-forming compounds.

Marquez, C.↗
DOE OSTI2021

Nondetection of Helium in the Upper Atmospheres of TRAPPIST-1b, e, and f

We obtained high-resolution spectra of the ultracool M-dwarf TRAPPIST-1 during the transit of its planet “b” using two high-dispersion near-infrared spectrographs, the Infrared Doppler (IRD) instrument on the Subaru 8.2m telescope, and the Habitable Zone Planet Finder (HPF) instrument on the 10 m Hobby–Eberly Telescope. These spectroscopic observations are complemented by a photometric transit observation for planet “b” using the APO/ARCTIC, which assisted us in capturing the correct transit times for our transit spectroscopy. Using the data obtained by the new IRD and HPF observations, as well as the prior transit observations of planets “b,” “e” and “f” from IRD, we attempt to constrain the atmospheric escape of the planet using the He i triplet 10830 Å absorption line. We do not detect evidence for any primordial extended H-He atmospheres in all three planets. To limit any planet-related absorption, we place an upper limit on the equivalent widths of <7.754 mÅ for planet “b,” <10.458 mÅ for planet “e,” <4.143 mÅ for planet “f” at 95% confidence from the IRD data, and <3.467 mÅ for planet “b” at 95% confidence from HPF data. Using these limits along with a solar-like composition isothermal Parker wind model, we attempt to constrain the mass-loss rates for the three planets. For TRAPPIST-1b, our models exclude the highest possible energy-limited rate for a wind temperature <5000 K. This nondetection of extended atmospheres with low mean-molecular weights in all three planets aids in further constraining their atmospheric composition by steering the focus toward the search of high-molecular-weight species in their atmospheres.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

Melt Processing Pretreatment Effects on Enzymatic Depolymerization of Poly(ethylene terephthalate)

Poly(ethylene terephthalate) (PET) is a common thermoplastic material, used in a wide variety of applications (i.e., bottles, fabrics, packaging, electronics, and automotive components). Increasing demand for PET has precipitated a need for improved recycling technology, especially for single-use PET waste. Recently, enzymatic depolymerization has shown promise as an environmentally responsible alternative for PET chemical recycling that yields economically useful products (e.g., terephthalic acid, adipic acid, and ethylene glycol). However, the depolymerization system still suffers from low rates on crystalline PET substrates, and effects of realistic waste streams are not known. In our work, PET waste is pretreated using an ultra-high-speed twin-screw extruder system. PET substrates were modified by various processing pretreatments to allow enzymes better access to depolymerize substrate materials. The effect of varying throughput and mechanical shear on structural properties of the PET waste was analyzed using molecular weight and thermal characterizations. These pretreated samples exhibit modifications in molecular weight, glass transition temperature, crystallinity, and specific surface area. The unpurified leaf-branch compost cutinase enzyme produced from the fed-batch fermentation of Escherichia coli BL21(DE3) was used in enzymatic depolymerization, where a faster reaction was observed as crystallinity was decreased and the specific surface area was increased. The rate of terephthalic acid production was also significantly higher for samples processed at lower mechanical shear with higher throughputs. As a result, this work demonstrates the potential for tailoring pretreatments in pursuit of faster and more energy efficient PET recycling using enzymes, with facile adaptation to the industrial scale for the circular economy.

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

Structure and dynamics of small polyimide oligomers with silicon as a function of aging

The effect of UV curing and shearing on the structure and behavior of a polyimide (PI) binder as it disperses silicon particles in a battery electrode slurry was investigated. PI dispersant effectiveness increases with UV curing time, which controls the overall binder molecular weight. Here, the shear force during electrode casting causes higher molecular weight PI to agglomerate, resulting in battery anodes with poorly dispersed Si particles that do not cycle well. It is hypothesized that when PI binder is added above a critical amount, it conformally coats the silicon particles and greatly impedes Li ion transport. There is an “interzonal region” for binder loading where it disperses silicon well and provides a coverage that facilitates Li transport through the anode material and into the silicon particles. These results have implications in ensuring reproducible electrode manufacturing and increasing cell performance by optimizing the PI structure and coordination with the silicon precursor.

36 MATERIALS SCIENCE↗
NASA NTRS1992

Oxidation of the N-terminal methionine of lens alpha-A crystallin

Antiserum against the N-terminal peptide of bovine alpha-A crystallin has been used to monitor purification of two different seropositive peptides (i.e. T1a and T1b) from a tryptic digest of bovine lens proteins. Both these peptides have similar amino acid compositions, but peptide T1b has a molecular weight 16 atomic mass units larger than T1a, suggesting posttranslational modification. Analysis of ionization fragments of the T1b peptide by mass spectrometry demonstrates that this difference in molecular weight is due to the in vivo oxidation of the N-terminal met residue of the alpha-A crystallin molecule.

NASA Discipline Cell Biology↗
NASA NTRS1990

Structure of the polymer-solvent interface

The first measurements of ellipticities from the liquid-liquid interface between polymer and solvent mixtures near their consolute points are reported. When scaled according to theory the ellipticities of high molecular weight polystyrene + solvent mixtures are consistent with those from simple, low molecular weight mixtures. The universal value of the scaled ellipticity is approximately 20 percent lower than that predicted by present theories.

Miles, Danny G., Jr.↗