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At least 289 records · Page 16

Applications of Quantum Chemistry to the Study of Carbon Nanotubes

For several years, scientists at NASA Ames have been studying the properties of carbon nanotubes using various experimental and computational methods. In this talk, I will compare different strategies for using quantum chemistry calculations to describe the electronic structure, deformation and chemical functionalization of single wall carbon nanotubes (SWNT) and the physisorption of small molecules on nanotube surfaces. The SWNT can be treated as an infinite (periodic) or finite length carbon cylinder or as a polycyclic aromatic hydrocarbon (PAH) molecule with an imposed curvature maintained by external constraints (as if it were cut out of the SWNT surface). Calculations are carried out using DFT and MP2 methods and a variety of atomic orbital basis sets from minimal (STO-3G) to valence triple zeta. The optimal approach is based on the particular SWNT property of interest. Examples to be discussed include: nanotube fluorination and other functionalization reactions; coating of nanotubes by water vapor and low-molecular weight organic molecules; and the nature of the interface between SWNT and liquids such as water and amines. In many cases, the quantum chemistry calculations are used to parameterize or validate force fields for molecular dynamics simulations. The results of these calculations have helped explain experimental data and contributed to the design of novel materials and sensors based on carbon nanotubes. Some of this research is described in the following papers:

Jaffe, Richard L.↗

Anhydrous Proton-Conducting Membranes for Fuel Cells

Polymeric electrolyte membranes that do not depend on water for conduction of protons are undergoing development for use in fuel cells. Prior polymeric electrolyte fuel-cell membranes (e.g., those that contain perfluorosulfonic acid) depend on water and must be limited to operation below a temperature of 125 C because they retain water poorly at higher temperatures. In contrast, the present developmental anhydrous membranes are expected to function well at temperatures up to 200 C. The developmental membranes exploit a hopping-and-reorganization proton- conduction process that can occur in the solid state in organic amine salts and is similar to a proton-conduction process in a liquid. This process was studied during the 1970s, but until now, there has been no report of exploiting organic amine salts for proton conduction in fuel cells.

Narayanan, Sekharipuram↗

Elucidating the Mechanism for the Reaction of $o$-Phthalaldehyde with Primary Amines in the Presence of Thiols

The use of o-phthalaldehyde (OPA) in combination with a thiol reagent is a common method for detecting primary amines in amino acids, peptides, and proteins. Despite its widespread use, the exact reaction mechanism has been debated since the 1980s. Here, we measure the kinetics of the reaction between OPA, alanine, and a dithiol (1,4-dithiolthreitol, DTT) as a function of pH and reagent concentration. Using these new measurements and accompanying kinetic models, we find evidence that the pH dependence of the kinetics arises from both the protonation states of alanine and DTT, the hydration state of OPA, and the unproductive equilibrium with DTT, all of which are pH-dependent. Importantly, these results support the mechanism originally proposed by Sternson [Rational design and evaluation of improved o-phthalaldehyde-like fluorogenic reagents. Anal. Biochem. 1985, 144, 233–246] and Wong [Reaction of o-phthalaldehyde with alanine and thiols: kinetics and mechanism. J. Am. Chem. Soc. 1985, 107, 6421–6422], in which the primary amine first reacts with OPA, followed by a reaction with the thiol to form the fluorescent isoindole product.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Divergent C–H Amidations and Imidations by Tuning Electrochemical Reaction Potentials

Electrochemical C–H functionalizations are attractive transformations, as they are capable of avoiding the use of transition metals, pre-oxidized precursors, or suprastoichiometric amounts of terminal oxidants. Herein an electrochemically tunable method was developed that enabled the divergent formation of cyclic amines or imines by applying different reaction potentials. Detailed cyclic voltammetry analyses, coupled with chronopotentiometry experiments, were carried out to provide insight into the mechanism, while atom economy was assessed through a paired electrolysis. Finally, selective C–H amidations and imidations were achieved to afford five- to seven-membered sulfonamide motifs that could be employed for late-stage modifications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Refining Processing Engines from SAPHIRE: Initialization of Fault Tree/Event Tree Solver

SAPHIRE has been extensively employed for over 35 years to model risk-important systems and quantify risk models. As a well-established and thoroughly documented Probabilistic Risk Assessment (PRA) tool, SAPHIRE has continuously tracked computational trends and received regular updates. Despite its ongoing evolution, there remains a need for further enhancements, particularly in dealing with the quantification of exceptionally large models. These improvements could take the form of algorithmic advancements, harnessing the power of parallel computing, and exploring the potential benefits of cloud computing solutions. Considering these aspirations, the notion of a remote solve option was introduced and subsequently evolved into a dedicated project within the SAPHIRE development team. A significant outcome of this initiative is SAPHSOLVE, an engine extracted from the SageRisk API designed specifically for remote solving capabilities. The ongoing project is nearing its culmination, marked by a series of discoveries that have brought undocumented aspects to light. Among these revelations is the intricacy of the input and output format for the SAPHSOLVE engine. This document serves the crucial purpose of meticulously delineating the precise formats for both input and output, as they form an indispensable foundation. The importance of documenting these formats cannot be overstated, as it is a pivotal step in facilitating rigorous testing and comparison. Whether it involves scrutinizing SAPHSOLVE results against those of the internal integrated solver or other external solvers, the ability to construct models or transform existing ones into a compatible SAPHSOLVE format is imperative. Chapter 1 offers a succinct introduction to both SAPHIRE and SAPHSOLVE, followed by Chapter 2 which outlines the roadmap for enhancing SAPHSOLVE. The core of this report is Chapter 3, which intricately elucidates the intricacies of the input and output file formats. To provide a tangible illustration of these formats, a rudimentary example has been compiled and is available in Appendix. SAPHSOLVE represents a novel external solving mechanism developed by the SAPHIRE team, although it has not yet reached the full spectrum of capabilities possessed by SAPHIRE's internal solver. However, the SAPHIRE team has set a comprehensive course for incorporating the functionalities of SAPHSOLVE. A comprehensive outlook on the future of SAPHSOLVE is expounded upon in Chapter 4.

97 MATHEMATICS AND COMPUTING↗

Spacesuit Portable Life Support System Breadboard (PLSS 1.0) Development and Test Results

A multi-year effort has been carried out at NASA-JSC to develop an advanced Extravehicular Activity (EVA) PLSS design intended to further the current state of the art by increasing operational flexibility, reducing consumables, and increasing robustness. Previous efforts have focused on modeling and analyzing the advanced PLSS architecture, as well as developing key enabling technologies. Like the current International Space Station (ISS) Extravehicular Mobility Unit (EMU) PLSS, the advanced PLSS comprises of three subsystems required to sustain the crew during EVA including the Thermal, Ventilation, and Oxygen Subsystems. This multi-year effort has culminated in the construction and operation of PLSS 1.0, a test rig that simulates full functionality of the advanced PLSS design. PLSS 1.0 integrates commercial off the shelf hardware with prototype technology development components, including the primary and secondary oxygen regulators, ventilation loop fan, Rapid Cycle Amine (RCA) swingbed, and Spacesuit Water Membrane Evaporator (SWME). Testing accumulated 239 hours over 45 days, while executing 172 test points. Specific PLSS 1.0 test objectives assessed during this testing include: confirming key individual components perform in a system level test as they have performed during component level testing; identifying unexpected system-level interactions; operating PLSS 1.0 in nominal steady-state EVA modes to baseline subsystem performance with respect to metabolic rate, ventilation loop pressure and flow rate, and environmental conditions; simulating nominal transient EVA operational scenarios; simulating contingency EVA operational scenarios; and further evaluating individual technology development components. Successful testing of the PLSS 1.0 provided a large database of test results that characterize system level and component performance. With the exception of several minor anomalies, the PLSS 1.0 test rig performed as expected; furthermore, many system responses trended in accordance with pre-test predictions.

Vogel, Matt R.↗

Structure of a dimeric photosystem II complex from a cyanobacterium acclimated to far-red light

Photosystem II (PSII) is the water-splitting enzyme central to oxygenic photosynthesis. To drive water oxidation, light is harvested by accessory pigments, mostly chlorophyll (Chl) a molecules, which absorb visible light (400–700 nm). Some cyanobacteria facultatively acclimate to shaded environments by altering their photosynthetic machinery to additionally absorb far-red light (FRL, 700–800 nm), a process termed far-red light photoacclimation or FaRLiP. During far-red light photoacclimation, FRL-PSII is assembled with FRL-specific isoforms of the subunits PsbA, PsbB, PsbC, PsbD, and PsbH, and some Chl-binding sites contain Chls d or f instead of the usual Chl a. The structure of an apo-FRL-PSII monomer lacking the FRL-specific PsbH subunit has previously been determined, but visualization of the dimeric complex has remained elusive. Here, we report the cryo-EM structure of a dimeric FRL–PSII complex. The site assignments for Chls d and f are consistent with those assigned in the previous apo-FRL-PSII monomeric structure. All sites that bind Chl d or Chl f at high occupancy exhibit a FRL-specific interaction of the formyl moiety of the Chl d or Chl f with the protein environment, which in some cases involves a phenylalanine sidechain. The structure retains the FRL-specific PsbH2 subunit, which appears to alter the energetic landscape of FRL-PSII, redirecting energy transfer from the phycobiliprotein complex to a Chl f molecule bound by PsbB2 that acts as a bridge for energy transfer to the electron transfer chain. Collectively, these observations extend our previous understanding of the structure-function relationship that allows PSII to function using lower energy FRL.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spacesuit Portable Life Support System Breadboard (PLSS 1.0) Development and Test Results

A multi-year effort has been carried out at the Johnson Space Center to develop an advanced EVA PLSS design intended to further the current state of the art by increasing operational flexibility, reducing consumables, and increasing robustness. This multi-year effort has culminated in the construction and operation of PLSS 1.0, a test rig that simulates full functionality of the advanced PLSS design. PLSS 1.0 integrates commercial off-the-shelf hardware with prototype technology development components, including the primary and secondary oxygen regulators, ventilation loop fan, Rapid Cycle Amine (RCA) swingbed, and Spacesuit Water Membrane Evaporator (SWME). PLSS 1.0 was tested from June 17th through September 30th, 2011. Testing accumulated 233 hours over 45 days, while executing 119 test points. An additional 164 hours of operational time were accrued during the test series, bringing the total operational time for PLSS 1.0 testing to 397 hours. Specific PLSS 1.0 test objectives assessed during this testing include: (1) Confirming prototype components perform in a system level test as they have performed during component level testing, (2) Identifying unexpected system-level interactions (3) Operating PLSS 1.0 in nominal steady-state EVA modes to baseline subsystem performance with respect to metabolic rate, ventilation loop pressure and flow rate, and environmental conditions (4) Simulating nominal transient EVA operational scenarios (5) Simulating contingency EVA operational scenarios (6) Further evaluating prototype technology development components Successful testing of the PLSS 1.0 provided a large database of test results that characterize system level and component performance. With the exception of several minor anomalies, the PLSS 1.0 test rig performed as expected. Documented anomalies and observations include: (1) Ventilation loop fan controller issues at high fan speeds (near 70,000 rpm, whereas the fan speed during nominal operations would be closer to 35,000 rpm) (2) RCA performance at boundary conditions, including carbon dioxide and water vapor saturation events, as well as reduced vacuum quality (3) SWME valve anomalies (4 documented cases where the SWME failed to respond to a control signal or physically jammed, preventing SWME control) (4) Reduction of SWME hollow fiber hydrophobicity and significant reduction of the SWME degassing capability after significant accumulated test time.

Watts, Carly A.↗

Development status of regenerable solid amine CO2 control systems

The development history of solid amine/water desorbed (SAWD) CO2 control systems is reviewed. The design of the preprototype SAWD I CO2 system on the basis of a three-man metabolic load at the 3.8 mm Hg ambient CO2 level, and the functions of the CO2 removal, CO2 storage/delivery, controller, and life test laboratory support packages are described. The development of a full-scale multiple canister SAWD II preprototype system, which is capable of conducting the CO2 removal/concentration function in a closed-loop atmosphere revitalization system during zero-gravity operation, is examined. The operation of the SAWD II system, including the absorption and desorption cycles, is analyzed. A reduction in the thermal mass of the canister and the system's energy transfer technique result in efficient energy use. The polyether foam, nylon felt, nickel foam, spring retained, and metal bellows bed tests performed to determine the design of the zero-gravity canister are studied; metal bellows are selected for the canister's configuration.

Colling, A. K., Jr.↗

Development of an Amine Oxide Polyzwitterion Brush Martini Model with Polarizable Water and Ions

Abstract In order to accurately simulate the fouling process of proteins onto polyzwitterion brushes, models that accurately capture the hydration properties and chain conformations of such brushes must first be established. We developed a Martini coarse-grained (CG) model for amine oxide polyzwitterion (PNOMA) brushes, a promising class of antifouling materials, in polarizable water and ions by fitting to all-atom bond and angle distributions, monomer hydration free energy, monomer–monomer distance potential of mean force (PMF), and monomer–salt radial distribution functions (RDFs). Martini 2.2P was selected for compatibility with the established polarizable water and ion models. For comparison with PNOMA, we also constructed models for conventional sulfobetaine (PSBMA) and phosphorylcholine (PMPC) polyzwitterions and the polycation PMETAC using established nonbonded bead types from the literature and refitting bond and angle potentials. We simulated each polymer brush chemistry for varying grafting density and chain length, validating brush height scaling relations against experimental data. The CG models captured the relative hydration strengths among different polyzwitterion chemistries, and brush heights extrapolated to higher molecular weights are in agreement with experimental ellipsometry data. We find that chain swelling of the superhydrophilic PNOMA brushes lies between that of the traditional polyzwitterions PSBMA/PMPC and the polycation PMETAC. For PNOMA brushes in NaCl solution, simulated brush height decreases with salt concentration due to the selectively strong interactions between amine oxide and sodium ions.

Walker, Christopher C. [Oak Ridge National Laborat↗

IR Spectra and Properties of Solid Acetone, an Interstellar and Cometary Molecule

Mid-infrared spectra of amorphous and crystalline acetone are presented along with measurements of the refractive index and density for both forms of the compound. Infrared band strengths are reported for the first time for amorphous and crystalline acetone, along with IR optical constants. Vapor pressures and a sublimation enthalpy for crystalline acetone also are reported. Positions of (sup 13) C-labeled acetone are measured. Band strengths are compared to gas-phase values and to the results of a density-functional calculation. A 73 percent error in previous work is identified and corrected.

ethers↗

A Structurally Diverse Compound Screening Library to Identify Substrates for Diamine, Polyamine, and Related Acetyltransferases

Spermidine/spermine N-acetyltransferases (SSATs) and other types of polyamine acetyltransferases (PAATs) acetylate diamines and/or polyamines. These enzymes are evolutionarily related and belong to the Gcn5-related N-acetyltransferase (GNAT) superfamily, yet we lack a fundamental understanding of their substrate specificity and/or promiscuity toward different compounds. Many of these enzymes are known or are predicted to acetylate polyamines, but in the cell there are other types of compounds that contain moieties derived from polyamines that may be the native substrates for these enzymes. To learn more about the identity of substrates that are acetylated, we selected and screened 17 different GNAT enzymes for activity toward a set of structurally diverse compounds that contained different types of amine moieties (e.g., aminopropyl, aminobutyl, etc.). These compounds included diamines, triamines, and polyamines containing primary amino groups, and they had structural diversity with variation of the chain length and presence or absence of internal amino groups and other functional groups. We found 12 of the 17 enzymes acetylated at least one of the compounds. Some enzymes were selective toward acetylating only one compound while others exhibited substrate promiscuity toward numerous compounds. Our experimental results ultimately allowed us to pinpoint specific substrates that could be further investigated to more fully understand substrate specificity versus promiscuity of GNAT enzymes and the role of acetylated small molecules in cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

CO 2 Capture Characteristics of Hyperbranched Poly(alkylene imine): A Molecular Dynamics Simulation Approach

This study explores the CO 2 capture characteristics of hyperbranched poly(ethylenimine) (HB-PEI) and poly- (propyleneimine) (HB-PPI) through molecular dynamics simulations using density functional theory-calibrated force fields. Key features such as density, free volume, glass transition temperature, CO 2 /H 2 O distribution, and molecular diffusion are systematically investigated to elucidate structure−function relationships under dry and hydrated conditions. HB-PEI demonstrates a slightly higher density and lower free volume compared to HB-PPI yet shows superior CO 2 capture due to the high amine concentration. Glass transition analysis indicates a higher thermal mobility in HBPEI, enhancing the CO 2 diffusivity. Pair correlation and coordination analyses confirm a stronger affinity of CO 2 with primary and secondary amines, particularly in hydrated environments where water competes with CO 2 for binding sites. Despite its more compact structure, HB-PEI outperformed HB-PPI in CO 2 and H 2 O transport, as confirmed by higher diffusion coefficients across all hydration levels. These findings highlight a critical balance among polymer architecture, amine accessibility, and hydration in designing next-generation solid amine sorbents for efficient direct air capture applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-throughput screening for discovery of benchtop separations systems for selected rare earth elements

Abstract Rare earth (RE) elements (scandium, yttrium, and the lanthanides) are critical for their role in sustainable energy technologies. Problems with their supply chain have motivated research to improve separations methods to recycle these elements from end of life technology. Toward this goal, we report the synthesis and characterization of the ligand tris[(1-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamido)ethyl]amine, H 3 1·TFA (TFA = trifluoroacetic acid), and complexes 1·RE (RE = La, Nd, Dy). A high-throughput experimentation (HTE) screen was developed to quantitatively determine the precipitation of 1·RE as a function of pH as well as equivalents of H 3 1·TFA. This method rapidly determines optimal conditions for the separation of RE mixtures, while minimizing materials consumption. The HTE-predicted conditions are used to achieve the lab-scale separation of Nd/Dy ( SF Nd/Dy = 213 ± 34) and La/Nd ( SF La/Nd = 16.2 ± 0.2) mixtures in acidic aqueous media.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reversible Photoswitching in Poly(2-oxazoline) Nanoreactors

This contribution reports light responsive catalytic nanoreactors based on poly(2-oxazoline) diblock copolymers. The hydrophobic block of the copolymer is a random copolymer consisting of a spiropyran functionalized 2-oxazoline (SPOx) and 2-(but-3-yn-1-yl)-4,5-dihydrooxazole (ButynOx), while the hydrophilic block is based on 2-methyl-2-oxazoline (MeOx). The block copolymer is terminated with tris(2-aminoethyl) amine (TREN) that serves as catalyst in a Knoevenagel condensation. Four block copolymers with different ButynOx/SPOx and hydrophilic/hydrophobic ratios are synthesized and self-assembled through solvent exchange. Micelles and vesicles of various sizes are observed by TEM, which undergo morphological and size changes in response to irradiation with UV light. We hypothesize that these transformations in the nanostructures are caused by increases in the hydrophilicity of the hydrophobic block when spiropyran (SP) isomerizes to merocyanine (MC) in the presence of UV light. The reversible transition from micellar to vesicular nanoreactors resulted in increased reaction kinetics through improved substrate accessibility to the catalytic site, or termination of the catalytic reaction due to polymer precipitation. Furthermore, these nanoreactors present a promising platform towards photoregulating reaction outcomes based on changes in nanostructure morphology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Search for the critical point of strongly-interacting matter in $^{40}$Ar + $^{45}$Sc collisions at 150A Ge V /c using scaled factorial moments of protons

The critical point of dense, strongly interacting matter is searched for at the CERN SPS in $^{40}$Ar + $^{45}$Sc collisions at 150A Ge V /c. The dependence of second-order scaled factorial moments of proton multiplicity distribution on the number of subdivisions of transverse momentum space is measured. The intermittency analysis is performed using both transverse momentum and cumulative transverse momentum. For the first time, statistically independent data sets are used for each subdivision number. The obtained results do not indicate any statistically significant intermittency pattern. An upper limit on the fraction of correlated proton pairs and the power of the correlation function is obtained based on a comparison with the Power-law Model developed for this purpose.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Targeting a cell surface vitamin D receptor on tumor-associated macrophages in triple-negative breast cancer

Triple-negative breast cancer (TNBC) is an aggressive tumor with limited treatment options and poor prognosis. We applied the in vivo phage display technology to isolate peptides homing to the immunosuppressive cellular microenvironment of TNBC as a strategy for non-malignant target discovery. We identified a cyclic peptide (CSSTRESAC) that specifically binds to a vitamin D receptor, protein disulfide-isomerase A3 (PDIA3) expressed on the cell surface of tumor-associated macrophages (TAM), and targets breast cancer in syngeneic TNBC, non-TNBC xenograft, and transgenic mouse models. Systemic administration of CSSTRESAC to TNBC-bearing mice shifted the cytokine profile toward an antitumor immune response and delayed tumor growth. Moreover, CSSTRESAC enabled ligand-directed theranostic delivery to tumors and a mathematical model confirmed our experimental findings. Finally, in silico analysis showed PDIA3-expressing TAM in TNBC patients. This work uncovers a functional interplay between a cell surface vitamin D receptor in TAM and antitumor immune response that could be therapeutically exploited.

59 BASIC BIOLOGICAL SCIENCES↗