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DOE OSTI2021

Building Neutron Scattering Infrastructure in Louisiana for Advanced Materials (Final Report)

The main objective of the Louisiana Consortium for Neutron Scattering (LaCNS) is to build a major neutron scattering infrastructure capable of treating both soft and hard materials. The goal is to create a sustainable effort having the quality, breadth, and depth necessary to produce competitive proposals including collaborative and center type proposals. Our scientific aim is to understand the role of coupling in emergent complex materials and its impact on the structure/property relationship and to explore how to tune the key couplings to guide the design of materials with the desired properties. This naturally includes building a base of users of the Spallation Neutron Source (SNS) and the High Flux Isotope Reactor (HFIR) in Louisiana; to train highly talented graduate and post-doctoral students in synthesis, neutron scattering, and simulation and modeling techniques, thereby helping to produce the next generation of scientist who use neutron scattering techniques as a crucial part of their research. The goal of our hard matter program is to understand the interplay between spin, charge, orbital, and lattice degrees of freedom in carefully selected complex materials. We have made considerable progress on number of complex systems including the oxide Sr3(Ru1-xMnx)2O7 where short-range magnetic ordering with anisotropic spin texture is initiated at the metal-insulator transition that clearly indicates a strong spin-charge coupling. Another critical area is in quantum materials. For example, in the topological semimetal BaMnSb2, we found a 3D canted antiferromagnetic Weyl semimetal with a 2D electronic structure and a nontrivial Berry phase. In addition, in the hexagonal chiral Mn1/3NbS2 system, we found soliton/soliton and soliton/antisoliton domain walls where the application of small fields or small currents can be used to control nanoscopic magnetic domains where the control of domain walls is crucially important for information storage. In addition, chemical transformation investigations were performed on the VISION instrument at Spallation Neutron Source (SNS). The soft matter effort was focused on understanding the role of non-covalent interactions on the structure and dynamics of fluid-based soft matter. One key focus was on sequence-defined (SD) amphiphilic peptoid polymers that allow encoding of molecular interactions and thereby systematic investigations of how charge directs the solution self-assembly of amphiphilic polymers in water. Another important area was on the dynamics of lipids self-assembled into membranes for exploring the permeability and mechanical using both neutron spin echo (NSE) spectroscopy and quasielastic neutron scattering (QENS) to distinguished between viscoelasticity and permeability at the molecular scale. Overall, the LaCNS project was quite successful, generating 145 publications and 245 presentations. Our graduate and post-doctoral students were well trained resulting in positions in national laboratories (Oak Ridge National Laboratory (ORNL), Argonne National Laboratory and Los Alamos National Laboratory), major research universities, and industry. We also developed a uniaxial pressure cell along with ORNL for SNS. A critical goal of this project was to establish a foundation for competing nationally in federally funded research programs. To this end, we were quite successful in generating over twenty-two federally and non-federally funded grants including awards from NSF, DOE, and DOD, and two early career awards. Equally important, we were able to secure a key major piece of instrumentation via a large ARO grant for a state-of-the-art electron microscope.

36 MATERIALS SCIENCE↗

NASA NTRS1991

Structure and functions of water-membrane interfaces and their role in proto-biological evolution

Among the most important developments in proto-biological evolution was the emergence of membrane-like structures. These are formed by spontaneous association of relatively simple amphiphilic molecules that would have been readily available in the primordial environment. The resulting interfacial regions between water and nonpolar interior of the membrane have several properties which made them uniquely suitable for promoting subsequent evolution. They can (1) selectively attract organic material and mediate its transport, (2) serve as simple catalysts for chemical reactions, and (3) promote the formation of trans-membrane electrical and chemical gradients which could provide energy sources for proto-cells. Understanding the structure of interfaces, their interactions with organic molecules and molecular mechanisms of their functions is an essential step to understanding proto-biological evolution. In our computer simulation studies, we showed that the structure of water at interfaces with nonpolar media is significantly different from that in the bulk. In particular, the average surface dipole density points from the vapor to the liquid. As a result, negative ions can approach the interface more easily than positive ions. Amphiphilic molecules composed of hydrocarbon conjugated rings and polar substituents (e.g., phenol) assume at the interface rigid orientations in which polar groups are buried in water while hydrocarbon parts are located in the nonpolar environment. These orientational differences are of special interest in connection with the ability of some of these molecules to efficiently absorb photons. Flexible molecules with polar substituents often adopt at interfaces conformations different from those in the bulk aquaeous solution and in the gas phase. As a result, in many instances both specificity and kinetics of chemical reactions in which these molecules can participate is modified by the presence of surfaces. Of special interest is the mechanism by which polar molecules are transferred across interface between water and a nonpolar medium. Our recent study showed that simple ionophores bind ions by the same mechanisms as ion channels and carriers from modern cells.

Pohorille, A.↗

NASA NTRS1992

Polycyclic aromatic hydrocarbons - Primitive pigment systems in the prebiotic environment

The chemical evolution of meteoritic organics in the primitive earth is examined experimentally with attention given to the photochemical effects of hydrocarbon/water mixtures. Also addressed are the generation of amphiphilic products by photochemical reactions and the transduction of light energy into potentially useful forms. Polycyclic aromatic hydrocarbons (PAHs) absorb light and exist in carbonaceous chondrites; PAHs are therefore examined as primitive pigments by means of salt solutions with pyrene, fluoranthene, and pyrene derivatives with hexadecane. The hexadecane undergoes photochemical oxidation and yields long-chain amphiphiles with oxygen supplied by water, and acid pH shifts also occur. PAHs are also tested in lipid bilayer membranes to examine light-energy transduction. Protons are found to accumulate within the membrane-bounded volume to form proton gradients, and this reaction is theorized to be a good model of primitive photochemical reactions that related to the transduction of light energy into useable forms.

Deamer, D. W.↗

NASA NTRS1999

Synthesis of Large Molecules in Cometary Ice Analogs: Physical Properties Related to Self-Assembly Processes

The combination of realistic laboratory simulations and infrared observations have revolutionized our understanding of interstellar dust and ice-the main component of comets. Since comets and carbonaceous micrometeorites may have been important sources of volatiles and carbon compounds on the early Earth, their organic composition may be related to the origin of life. Ices on grains in molecular clouds contain a variety of simple molecules. The D/H ratios of the comets Hale-Bopp and Hyakutake are consistent with a primarily interstellar ice mixture. Within the cloud and especially in the presolar nebula through the early solar system, these icy grains would have been photoprocessed by the ultraviolet producing more complex species such as hexamethylenetetramine, polyoxymethylenes, and simple keones. We reported at the 1999 Bioastronomy meeting laboratory simulations studied to identify the types of molecules which could have been generated in pre-cometary ices. Experiments were conducted by forming a realistic interstellar mixed-molecular ice (H2O, CH3OH, NH3 and CO) at approximately 10 K under high vacuum irradiated with UV light from a hydrogen plasma lamp. The gas mixture was typically 100:50:1:1, however when different ratios were used material with similar characteristics was still produced. The residue that remained after warming to room temperature was analyzed by HPLC, and by several mass spectrometric methods. This material contains a rich mixture of complex compounds with mass spectral profiles resembling those found in IDPs and meteorites. Surface tension measurements show that an amphiphilic component is also present. These species do not appear in various controls or in unphotolyzed samples. Residues from the simulations were also dispersed in aqueous media for microscopy. The organic material forms 10-40 gm diameter droplets that fluoresce at 300-450 nm under UV excitation. These droplets have a morphology and internal structure which appear strikingly similar to those produced by extracts of the Murchison meteorite. Together, these results suggest a link between organic material photochemically synthesized on the cold grains in dense, interstellar molecular clouds and compounds that may have contributed to the organic inventory of the primitive Earth. For example, the amphiphilic properties of such compounds permit self-assembly into the membranous boundary structures that required for the first forms of cellular life.

Dworkin, Jason P.↗

NASA NTRS2000

Surfactant Facilitated Spreading of Aqueous Drops on Hydrophobic Surfaces

Microgravity technologies often require aqueous phases to spread over nonwetting hydrophobic solid/surfaces. At a hydrophobic surface, the air/hydrophobic solid tension is low, and the solid/aqueous tension is high. A large contact angle forms as the aqueous/air tension acts together with the solid/air tension to balance the large solid/aqueous tension. The aqueous phase, instead of spreading, is held in a meniscus by the large angle. Surfactants facilitate the wetting of water on hydrophobic surfaces by adsorbing on the water/air and hydrophobic solid/water interfaces and lowering the surface tensions of these interfaces. The tension reductions decrease the contact angle, which increases the equilibrium wetted area. Hydrocarbon surfactants (i.e. amphiphiles with a hydrophobic chain of methylene groups attached to a large polar group to give aqueous solubility) do not reduce significantly the contact angles of the very hydrophobic surfaces such as parafilm or polyethylene. Trisiloxane surfactants (amphiphiles with a hydrophobe consisting of methyl groups linked to a trisiloxane backbone in the form of a disk ((CH3)3-Si-O-Si-O-Si(CH3)3)) and an extended ethoxylate (-(OCH2CH2)n-) polar group in the form of a chain with seven or eight units) can significantly reduce the contact angle of water on a very hydrophobic surface and cause rapid and complete (or nearly complete) spreading (lermed superspreading). The overall goal of the research described in this proposal is to establish and verify a theory for how trisiloxanes cause superspreading, and then use this knowledge as a guide to developing more general hydrocarbon based surfactant systems which superspread and can be used in microgravity. We propose that the trisiloxane surfactants superspread when the siloxane adsorbs, the hydrophobic disk parts of the molecule adsorb onto the surface removing the surface water. Since the cross sectional area of the disk is larger than that of the extended ethoxylate chain, the disks can form a space filling mat on the surface which removes a significant amount of the surface water. The water adjacent to the hydrophobic solid surface is of high energy due to incomplete hydrogen bonding; its removal significantly lowers the tension and reduces the contact angle. Hydrocarbon surfactants cannot remove as much surface water because their large polar groups prevent the chains from cohering lengthwise. In our report last year we presented a poster describing the preparation of model very hydrophobic surfaces which are homogeneous and atomically smooth using self assembled monolayers of octadecyl trichlorosilane (OTS). In this poster we will use these surfaces as test substrates in developing hydrocarbon based surfactant systems which superspread. We studied a binary hydrocarbon surfactant systems consisting of a very soluble large polar group polyethylene oxide surfactant (C12E6 (CH3(CH2)11(OCH2CH2)6OH) and a long chain alcohol dodecanol. By mixing the alcohol with this soluble surfactant we have found that the contact angle of the mixed system on our test hydrophobic surfaces is very low. We hypothesize that the alcohol fills in the gaps between adjacent adsorbed chains of the large polar group surfactant. This filling in removes the surface water and effects the decrease in contact angle. We confirm this hypothesis by demonstrating that at the air/water interface the mixed layer forms condensed phases while the soluble large polar group surfactant by itself does not. We present drop impact experiments which demonstrate that the dodecanol/C12E6 mixture is effective in causing impacting drops to spread on the very hydrophobic model OTS surfaces.

Kumar, Nitin↗

NASA NTRS2001

Simulation of Peptides at Aqueous Interfaces

Behavior of peptides at water-membrane interfaces is of great interest in studies on cellular transport and signaling, membrane fusion, and the action of toxins and antibiotics. Many peptides, which exist in water only as random coils, can form sequence-dependent, ordered structures at aqueous interfaces, incorporate into membranes and self-assembly into functional units, such as simple ion channels. Multi -nanosecond molecular dynamics simulations have been carried out to study the mechanism and energetics of interfacial folding of both non-polar and amphiphilic peptides, their insertion into membranes and association into higher-order structures. The simulations indicate that peptides fold non-sequentially, often through a series of amphiphilic intermediates. They further incorporate into the membrane in a preferred direction as folded monomers, and only then aggregate into dimers and, possibly, further into "dimers of dimers".

Pohorille, Andrew↗

NASA NTRS2001

Surfactant Facilitated Spreading of Aqueous Drops on Hydrophobic Surfaces

Microgravity technologies often require aqueous phases to spread over nonwetting hydrophobic solid surfaces. Surfactants facilitate the wetting of water on hydrophobic surfaces by adsorbing on the water/air and hydrophobic solid/water interfaces and lowering the surface tensions of these interfaces. The tension reductions decrease the contact angle, which increases the equilibrium wetted area. Hydrocarbon surfactants; (i.e., amphiphiles with a hydrophobic moiety consisting of an extended chain of (aliphatic) methylene -CH2- groups attached to a large polar group to give aqueous solubility) are capable of reducing the contact angles on surfaces which are not very hydrophobic, but do not reduce significantly the contact angles of the very hydrophobic surfaces such as parafilm, polyethylene or self assembled monolayers. Trisiloxane surfactants (amphiphiles with a hydrophobe consisting of methyl groups linked to a trisiloxane backbone in the form of a disk ((CH3)3-Si-O-Si-O-Si(CH3)3) and an extended ethoxylate (-(OCH2CH2)a-) polar group in the form of a chain with four or eight units) can significantly reduce the contact angle of water on a very hydrophobic surface and cause rapid and complete (or nearly complete) spreading (termed superspreading). The overall goal of the research described in this proposal is to establish and verify a theory for how trisiloxanes cause superspreading, and then use this knowledge as a guide to developing more general hydrocarbon based surfactant systems which superspread. We propose that the trisiloxane surfactants superspread because their structure allows them to strongly lower the high hydrophobic solid/aqueous tension when they adsorb to the solid surface. When the siloxane adsorbs, the hydrophobic disk parts of the molecule adsorb onto the surface removing the surface water. Since the cross-sectional area of the disk is larger than that of the extended ethoxylate chain, the disks can form a space-filling mat on the surface which removes a significant amount of the surface water. In this presentation, we report the results of measurements of the molecular packing and rates of kinetic exchange of the trisiloxane surfactants at the air/water interface in order to confirm our picture of trisiloxane packing, and provide additional insight into the superspreading process. We used the pendant bubble technique as a Langmuir trough to measure the trisiloxane equation of state which relates the tension to the surface concentration. From these measurements we obtain accurate values for the maximum packing density. We find that trisiloxanes with 4 and 8 ethoxylate groups have the same maximum packing concentration, indicating that the maximum packing is controlled by the cross section of the head group. For trisiloxanes with larger than eight ethoxylates, the maximum packing increases with ethoxylate number, indicating that the disposition of the ethoxylate chain (i.e., its effective size) is controlling. This supports our picture of superspreading: The superspreading ability of trisiloxanes decreases considerably for trisiloxanes with larger than eight ethoxylates; the packing measurements indicate that for the higher ethoxylate number trisiloxanes, the compact nonpolar head groups are pushed apart by the ethoxylate chain. They leave spaces of surface water on adsorption and do not lower the solid tension as much as their lower chain analogues. Finally the report measurements of the dynamic tension reduction accompanying the adsorption of trisiloxanes onto an initially clean interface using the pendant bubble technique, and we obtain from these relaxations, the equation of state and a mass transfer model, the rate constants for kinetic exchange. We find that the rate constants for desorption of trisiloxanes are generally much slower than for analogous aliphatic polyethoxylate surfactants with identical ethoxylate chain lengths. When an aqueous drop of a superspreader solution is placed on a hydrophobic surface and begins to spread, the lower desorption rates allows the tension at the drop center to remain reduced relative to the tension of the expanding periphery, thus strengthening Marangoni forces which can assist the spreading. Marangoni forces can be especially significant in the case of superspreaders because their maximum equilibrium reduction in tension is several dynes/cm lower than for aliphatic surfactants.

Kumar, Nitin↗

NASA NTRS2004

The First Cell Membranes

Organic compounds are synthesized in the interstellar medium and can be delivered to planetary surfaces such as the early Earth, where they mix with endogenous organic mixtures. Some of these compounds are amphiphilic, having polar and non-polar groups on the same molecule. Amphiphilic compounds spontaneously self-assembly into more complex structures such as bimolecular layers, which in turn form closed membranous vesicles. The first forms of cellular life required self-assembled membranes that were likely to be available on the prebiotic Earth. Laboratory simulations show that such vesicles readily encapsulate functional macromolecules, including nucleic acids and polymerases. A goal of future investigations is to fabricate artificial cells as models of the origin of life.

Deamer, David↗

NASA NTRS1993

Viewpoint 9--molecular structure of aqueous interfaces

In this review we summarize recent progress in our understanding of the structure of aqueous interfaces emerging from molecular level computer simulations. It is emphasized that the presence of the interface induces specific structural effects which, in turn, influence a wide variety of phenomena occurring near the phase boundaries. At the liquid-vapor interface, the most probable orientations of a water molecule is such that its dipole moment lies parallel to the interface, one O-H bond points toward the vapor and the other O-H bond is directed toward the liquid. The orientational distributions are broad and slightly asymmetric, resulting in an excess dipole moment pointing toward the liquid. These structural preferences persist at interfaces between water and nonpolar liquids, indicating that the interactions between the two liquids in contact are weak. It was found that liquid-liquid interfaces are locally sharp but broadened by capillary waves. One consequence of anisotropic orientations of interfacial water molecules is asymmetric interactions, with respect to the sign of the charge, of ions with the water surface. It was found that even very close to the surface ions retain their hydration shells. New features of aqueous interfaces have been revealed in studies of water-membrane and water-monolayer systems. In particular, water molecules are strongly oriented by the polar head groups of the amphiphilic phase, and they penetrate the hydrophilic head-group region, but not the hydrophobic core. At infinite dilution near interfaces, amphiphilic molecules exhibit behavior different from that in the gas phase or in bulk water. This result sheds new light on the nature of hydrophobic effect in the interfacial regions. The presence of interfaces was also shown to affect both equilibrium and dynamic components of rates of chemical reactions. Applications of continuum models to interfacial problems have been, so far, unsuccessful. This, again, underscores the importance of molecular-level information about interfaces.

Review, Tutorial↗

NASA NTRS2009

The Origin of Primitive Cells, Nutrient Intake, and Non-Enzymatic Elongation of Encapsulated Nucleotides

Fatty acids and fatty alcohols are commonly found in experiments simulating the prebiotic 'soup'. These amphiphiles can be synthesized under prebiotic conditions, at least as long as the molecules are chemically relatively simple and do not need to be enantiomerically pure. In the context of topical origin-of-life theories, two distinct formation pathways for amphiphiles have been described; one related to geophysical sites, such as marine hydrothermal systems, and another to extraterrestrial sources, such as the proto-solar nebula, which was fed by interplanetary and interstellar nebulae. The chemical analysis of each provides individual characteristic challenges.

Meierhenrich, Uwe J.↗

NASA NTRS2006

Stable Carbon Isotopic Signatures of Abiotic Organics from Hydrothermal Synthesis Experiments

Stable carbon isotopes can be powerful biogeochemical markers in the study of life's origins. Biogenic carbon fixation produces organics that are depleted in C-13 by about -20 to -30%0. Less attention has been paid to the isotopic signatures of abiotic processes. The possibility of abiotic processes producing organics with morphologies and isotopic signatures in the biogenic range has been at the center of recent debate over the Earth's earliest microfossils. The abiotic synthesis of organic compounds in hydrothermal environments is one possible source of endogenous organic matter to the prebiotic earth. Simulated hydrothermal settings have been shown to synthesize, among other things, single chain amphiphiles and simple lipids from a mix of CO, CO2, and H2. A key characteristic of these amphiphilic molecules is the ability to self-assemble in aqueous phases into more organized structures called vesicles, which form a selectively permeable boundary and serve the function of containing and concentrating other organic molecules. The ability to form cell like structures also makes these compounds more likely to be mistaken for biogenic. Hydrothermal simulation experiments were conducted from oxalic or formic acid in water at 175 C for 72 hr. The molecular and isotopic composition of the products of these reactions were determined and compared to biogenic fractionations . Preliminary results indicate isotopic fractionation during abiotic hydrocarbon synthesis in hydrothermal environments is on par with biological carbon fixation.

Stern, Jennifer C.↗

NASA NTRS2016

Sugar and Sugar Derivatives in Residues Produced from the UV Irradiation of Astrophysical Ice Analogs

A large variety and number of organic compounds of prebiotic interest are known to be present in carbonaceous chondrites. Among them, one sugar (dihydroxyacetone) as well as several sugar acids, sugar alcohols, and other sugar derivatives have been reported in the Murchison and Murray meteorites. Their presence, along with amino acids, amphiphiles, and nucleobases strongly suggests that molecules essential to life can form abiotically under astrophysical conditions. This hypothesis is supported by laboratory studies on the formation of complex organic molecules from the ultraviolet (UV) irradiation of simulated astrophysical ice mixtures consisting of H2O, CO, CO2, CH3OH, CH4, NH3, etc., at low temperature. In the past 15 years, these studies have shown that the organic residues recovered at room temperature contain amino acids, amphiphiles, nucleobases, as well as other complex organics. However, no systematic search for the presence of sugars and sugar derivatives in laboratory residues have been reported to date, despite the fact that those compounds are of primary prebiotic significance. Indeed, only small (up to 3 carbon atoms) sugar derivatives including glycerol and glyceric acid have been detected in residues so far.

Ice Irradiation↗

NASA NTRS2017

Sugars and Sugar Derivatives in Residues Produced from the UV Irradiation of Astrophysical Ice Analogs

Carbonaceous chondrites contain a large variety of organic compounds of prebiotic interest, which include amino acids, amphiphiles, nucleobases, and sugar derivatives. The presence of these compounds strongly suggests that molecules essential to life can form abiotically under astrophysical conditions. Among the sugar derivatives reported in the Murchison and Murray meteorites, only one sugar (dihydroxyacetone) was found, together with a variety of sugar alcohols and sugar acids containing up to 6 carbon atoms, including sugar acid derivatives of the biological sugars ribose and glucose. On the other hand, laboratory studies on the formation of complex organic molecules from the ultraviolet (UV) irradiation of simulated astrophysical ice mixtures consisting of H2O, CO, CO2, CH3OH, CH4, NH3, etc., at low temperature have been routinely carried out in the past 15 years. These studies have shown that the organic residues recovered at room temperature contain amino acids, amphiphiles, nucleobases, as well as other complex organics, supporting a scenario in which molecules of prebiotic interest can form in extra-terrestrial environments.

Astrochemistry↗

NASA NTRS2017

Sugar Derivatives in Residues Produced from the UV Irradiation of Astrophysical Ice Analogs

A large variety of organic compounds of astrobiological and prebiotic interest have been detected in carbonaceous meteorites. These include amino acids, carboxylic acids, amphiphiles, functionalized nitrogen heterocycles such as nucleobases, functionalized polycylic aromatic hydrocarbons such as quinones, and sugar derivatives. The sugar derivatives identified in the Murchison and Murray meteorites are mainly sugar alcohols and sugar acids, and only the smallest sugar (dihydroxyacetone) has been detected. The presence of such a variety of organics in meteorites strongly suggests that molecules essential to life can form abiotically under astrophysical conditions. This hypothesis is further supported by laboratory studies in which astrophysical ice analogs (mixtures of H2O, CO, CO2, CH3OH, CH4, NH3, etc.) are subjected to ultraviolet (UV) irradiation at low temperature (<15 K) to simulate cold interstellar environments. These studies show that the organic residues recovered at room temperature after irradiation contain amino acids, amphiphiles, nucleobases, sugar derivatives, as well as other complex organic compounds. The finding of such compounds under plausible interstellar conditions is consistent with the presence of organic compounds in meteorites. Until very recently, no systematic search for the presence of sugar derivatives in laboratory residues had been carried out. The detection of ribose, the sugar constituent of RNA in all living systems, as well as other sugars, sugar alcohols, and sugar acids have been recently reported in one organic residue produced from the UV irradiation of an H2O:CH3OH:NH3 (10:3.5:1) ice mixture at 80 K. In this work, we present a detailed study of organic residues produced from the UV irradiation ice mixtures of several starting compositions (containing H2O, CH3OH, CO, CO2, and/or NH3) at <15 K for their sugar derivative content. Our results confirm the presence of all 3C‒5C sugar alcohols, several 3C‒5C sugars, and all 3C‒4C sugar acids (in decreasing order of abundances) in the residues. The higher abundances of sugar alcohols in these residues suggest a pathway in which sugar alcohols are formed first, while the formation of sugars and sugar acids require more steps. Finally, our results are compared with the detection of sugars derivatives in primitive meteorites.

Astrophysical Ice Analogs↗

NASA NTRS2015

Search for Sugars and Related Compounds in Residues Produced from the UV Irradiation of Astrophysical Ice Analogs

A large variety and number of organic compounds of prebiotic interest have been detected in meteorites. Among them, one sugar (dihydroxyacetone) as well as several sugar acids and sugar alcohols have been detected in Murchison and Murray [1]. Their presence in meteorites, along with amino acids, amphiphiles, and nucleobases [2-6], strongly suggests that molecules essential to life can form abiotically under astrophysical conditions. This hypothesis is supported by laboratory studies on the formation of complex organic molecules from the ultraviolet (UV) irradiation of astrophysical ice analogs (H2O, CO, CO2, CH3OH, CH4, NH3, etc.). These studies show that the organic residues recovered at room temperature after the UV irradiation of such ice mixtures contain amino acids [7-9], amphiphiles [4], nucleobases [10-13], and other organic complex organic compounds [14-16]. However, no systematic search for the presence of sugars, sugar acids, and sugar alcohols in laboratory residues have been reported to date, despite the fact that those compounds are involved in a large number of biological processes. Only a limited number of small (less than or equal to 3 carbon atoms) sugar derivatives such as glycerol and glyceric acid have been detected in residues [14-16]. In this work, we show results obtained from the systematic search for sugars and sugar-related compounds in organic residues produced from the UV irradiation of simple CH3OH and H2O+CH3OH ices, and more astrophysically relevant ice mixtures containing H2O, CH3OH, CO, and NH3. The results are compared with measurements of sugars and related compounds in primitive meteorites.

Murchison and Murray↗

DOE OSTI2020

Heme peptide materials for anti-inflammatory regenerative nanobiomedicine

Heme released as a result of sustained injury leads to toxicity and triggers an inflammatory response and tissue damage. Heme oxygenase, an enzyme, recognizes, binds free heme and breaks it down as a part of the anti-inflammatory response. The present disclosure relates to a class of peptide amphiphiles that mimic the heme oxygenase function, and have shown that the designed peptide is able to bind and break down heme thus validating its potential as an anti-inflammatory agent that promotes tissue repair and useful in wound healing. The disclosed peptide sequence design provides control of amphiphile peptides' supramolecular structure and function. Applicants have shown that the incorporated heme molecule can transport CO, which suggests that the peptides can also transport NO, O2 and reactive oxygens, the molecules which are responsible for vasodilation, neurotransmission and cell death. Besides heme oxygenase function, it is believed that the designed peptides can recognize normal tissue adjacent to the damaged area and the peptide can self-assemble into fibers that promote healthy cell growth.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Rigid Supramolecular Aramid Nanotubes as Catalyst Supports

Solution‐phase heterogeneous catalysts benefit from nanoscale dimensions, which maximize specific surface area and enhance catalytic activity. However, the ease of recovering such nanocatalysts depends on the design of the support materials, which are often particle‐like. Rigid 1D nanomaterials are proposed as supports that can enhance separability while offering high volumetric specific surface area for greater catalyst loading and activity. Here, aramid amphiphiles (AAs) are designed to spontaneously self‐assemble in water into high‐aspect‐ratio supramolecular nanotubes with tunable surface chemistry. These AA nanotubes exhibit high persistence lengths (P = 750 ± 340 µm) and mechanical stiffnesses (3 N/m). Incorporating surface thiol groups enables immobilization of catalytic gold nanoparticles. The resulting AA nanotube‐gold nanoparticle complexes exhibit high catalytic activity, efficient recoverability via simple microfiltration, and sustained reusability over ten reaction cycles. This study demonstrates the utility of molecular self‐assembled 1D nanomaterials as versatile scaffolds for the reuse and recovery of nanoscale catalysts.

1D nanomaterials↗

DOE OSTI2023

Artificial extracellular matrix scaffolds of mobile molecules enhance maturation of human stem cell-derived neurons

Human induced pluripotent stem cell (hiPSC) technologies offer a unique resource for modeling neurological diseases. However, iPSC models are fraught with technical limitations including abnormal aggregation and inefficient maturation of differentiated neurons. These problems are in part due to the absence of synergistic cues of the native extracellular matrix (ECM). We report on the use of three artificial ECMs based on peptide amphiphile (PA) supramolecular nanofibers. All nanofibers display the laminin-derived IKVAV signal on their surface but differ in the nature of their non-bioactive domains. Here, we find that nanofibers with greater intensity of internal supramolecular motion have enhanced bioactivity toward hiPSC-derived motor and cortical neurons. Proteomic, biochemical, and functional assays reveal that highly mobile PA scaffolds caused enhanced β1-integrin pathway activation, reduced aggregation, increased arborization, and matured electrophysiological activity of neurons. Our work highlights the importance of designing biomimetic ECMs to study the development, function, and dysfunction of human neurons.

60 APPLIED LIFE SCIENCES↗