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Membrane Adsorbents Comprising Self-Assembled Inorganic Nanocages (SINCs) for Super-fast Direct Air Capture Enabled by Passive Cooling

The objectives of the proposed project were to develop highly porous membrane adsorbents comprising CO 2 -philic polymers and self-assembled inorganic nanocages (SINCs) for rapid temperature swing adsorption using electricity-free solar heating and radiative cooling, enabling an economically viable approach for direct air capture (DAC). Our core technical activities combine three key innovations. (1) Highly porous flat-sheet membrane adsorbents contain CO 2 -philic amines that can be easily produced using a phase inversion method. (2) CO 2 -philic SINCs can be easily dispersed in the polymers with great stability (compared with the metal-organic frameworks or MOFs). (3) The adsorption and desorption are integrated with solar heating and radiative cooling for rapid continuous operation, in contrast to traditional long-cycle separate operation. The membrane adsorbents containing amines, polymers, and SINCs were produced using a one-step industrial process. The porous membranes coupled with porous SINCs offer low resistance for gas flow and fast CO 2 sorption/desorption cycles, while the incorporation of the additional amine groups provides high CO 2 sorption capacity. The key achievements are summarized below. (1) Membrane adsorbents with high PEI loading (>40%), high porosity of >80%, and low gasflow resistance were prepared in one step using commercially available, low-cost materials. (2) Membrane adsorbents based on Solupor and PEI show CO 2 sorption capacity of >1.5 mmol/g using air containing 400 ppm at a relative humidity of 15%. (3) Effect of the adsorbent compositions (such as PEI type, PEI content, SINC content, porosity) on the CO 2 sorption was systematically investigated. (4) Effect of the processing conditions (such as CO 2 content, temperature, and relative humidity) on the CO 2 sorption was systematically investigated; (5) The stability of the membrane adsorption against many cycles of sorption and desorption was studied. The higher molecular weight of PEI (PEI25k) shows better stability than PEI800. (6) Advanced materials with radiative cooling were developed, which can decrease the temperature by 5-7 °C compared to the ambient temperature. (7) Preliminary techno-economic analysis shows that our process may achieve a capture cost of $1,343/tonne CO 2 with a total OPEX cost of $1,112/tonne CO 2 . The adsorbent replacement cost accounted for 52% of the total OPEX cost. Membrane adsorbents with lower costs and longer operation life can significantly decrease the cost. The proposed project directly addresses the requirement of DE-FOA-0002188, i.e., novel materials with CO 2 adsorption capacity for direct air capture with integrated solar heating and radiative cooling to reduce the cost of the DAC. Our future work will focus on the development of low-cost adsorbents that can be stable at the sorption and desorption conditions for long term.

14 SOLAR ENERGY↗

Direct Air Capture of CO 2 and Delivery to Photobioreactors for Algal Biofuel Production (Final Report)

A mobile DAC system was designed and constructed to pair with photobioreactors growing algae for biofuel production. The DAC system was designed as a versatile research system, rather than a compact production unit. The system was constructed and mounted on a mobile skid to facilitate transportation to the algae production site. Within the DAC system, CO 2 was captured using amine-loaded monoliths that allow for high CO 2 uptake with low pressure drop. The CO 2 is collected using a Global Thermostat patented temperature/vacuum swing adsorption (TVSA) process. Amine sorbents and process conditions were optimized to produce 10 to >20 g CO 2 .h-1. The stability of the amine sorbents was also studied, with sorbent modifications made to improve stability to degradation by oxidation. An Algenol-developed Spirulina strain (Arthrospira platensis AB2293) was selected as the production cyanobacterial strain. AB2293 cultured was inoculum for outdoor production following PBR installation by Algenol. The PBR system was composed of three independent PBRs, with each PBR composed of four hanging bags internally recirculated by a liquid turnover pump. The PBRs were operated outdoors in Atlanta, GA, and integrated with the DAC system. Algae were grown with similar productivity using DAC-CO 2 as algae grown using pure CO 2 obtained commercially (Airgas). Throughout the experimental duration, no discoloration was observed, and cellular morphology was consistent between the two experimental treatments. An LCA including lifecycle greenhouse gas emissions, full life cycle inventory of the Algenol system and the DAC system and integrated DAC+PBR system was developed. Lifecycle greenhouse gas emissions were calculated for capture of carbon dioxide using input from Global Thermostat and the National Renewable Energy Laboratory. Three scenarios for energy provision were evaluated: a natural gas combined heat and power system sized to meet the electricity requirement, a natural gas combined heat and power system sized to meet the process heat requirements, and a system without on-site power that procures the electricity from the grid. In all three cases, as expected, the major contributor to the emissions is the energy consumption associated with the desorption step of the DAC process. The LCA quantified the reduced potential energy and greenhouse gas emissions of heat and mass integration of DAC and Algenol compared to unintegrated DAC and Algenol systems. A life cycle assessment of the role of sorbent productivity and lifetime was also developed. The development of more robust, oxidation resistant DAC sorbents may enable small reductions in energy requirements and in lifecycle greenhouse gas emissions and other environmental impacts. NREL performed techno-economic analysis (TEA) to identify the integration scenario most likely to achieve a 15% cost reduction target versus the baseline. Heat and mass integration of DAC and the PBR is critical to minimizing the MFSP. The baseline case utilizes no heat and mass integration, and the DAC system provides 100% of the CO 2 required by the photobioreactors (20 tonnes/hr), operating for 12 hours/day capturing 40 tonnes CO 2 /operating hour. The minimum fuel selling price (MFSP) of ethanol calculated from the baseline case was $10.68/gal ethanol. This corresponds with a targeted MFSP of $9.07/gal ethanol (or 15% reduction). This target was achieved by integration Option 2a with the greatest cost reduction of 17.8% (or $8.78/gal) and integration Option 2b with a cost reduction of 16.4% (or $8.93/gal). Reductions in MFSP are attributed to two primary process considerations: (a) CO 2 storage at night reduces the capital expenses associated with DAC (i.e., increasing on-stream time); and (b) distributed DAC scenarios (DAC-PBR integration Options 2a and 2b) make use of boiler and DAC CHP flue gas CO 2 (free). Direct air capture on-stream time was one of the largest contributors to MFSP reduction.

09 BIOMASS FUELS↗

High Performance Solvent for NGCC Flue Gas CO 2 Capture (Final Technical Report)

Amine-based solvent absorption is the most mature and reliable technology for large scale CO 2 capture, dating back to the 1930s when monoethanolamine (MEA) was used to treat acid gases from oil refineries. However, while strategic advancements have optimized the CO2 capture process, the cost of capture remains high, where current estimates suggest that CO 2 capture costs are around $\$$72/tonne of CO 2 . To address this, solvent development and optimization have become a focus of current research. This project sought to develop a high-performance solvent to reduce the overall cost of CO 2 capture from NGCC flue gas. Here, solvent optimization focused on: (1) reducing the energy required for CO 2 desorption in a reboiler, (2) improving CO 2 absorption and desorption reaction kinetics, (3) improving solvent stability, and (4) reducing environmental impacts. Susteon has developed and evaluated a promoted solvent, Sustenol™, for NGCC flue gas CO 2 capture. The optimized Sustenol™ also shows a higher dynamic CO 2 absorption capacity of ~0.5 mol CO2 /mol amine compared to 0.25 mol CO2 /mol amine for 30 wt% MEA. Additionally, the solvent is oxidatively, thermally and hydrothermally stable, which leads to lower solvent loss and emissions. These advancements have resulted in a solvent regeneration energy of 2.16 GJ/tonne of CO 2 which is >30% lower than current state-of-the-art commercial and emerging solvents. Combined with empirical data from the bench and pilot scale testing, this preliminary TEA study indicated the cost of CO 2 capture by Sustenol™ for 97% CO 2 removal at $\$$54/tonne and for 90% removal at $\$$49/tonne, with a pathway to achieve $\$$45/tonne of CO 2 with continued process and solvent advancements. Susteon has developed a technology roadmap to reduce the cost of CO 2 capture to <$\$$45/tonne for NGCC flue gas. Susteon plans to derisk this technology for commercial deployment through comprehensive solvent degradation testing, long-term testing in a pilot plant at 5 tonne CO2 /day and demonstration scale testing at 100 tonne CO2 /day with NGCC flue gas and engineering design studies to qualify Sustenol™ as a drop-in replacement solvent.

03 NATURAL GAS↗

Host Design for Carbon Capture and Regeneration in Porous Liquids

The demand for efficient gas capture technologies drives the exploration of porous liquids (PLs) as alternatives to traditional amine mixtures, which incur high operational costs due to energy-intensive regeneration processes. This research investigates the use of porous organic cages (POCs) within PLs to enhance gas capture and separation capabilities. We demonstrate that the flexibility of POCs under isostatic pressure facilitates the expulsion of captured gas molecules, enabling low-energy regeneration and the creation of an isostatic pressure testing capability for PLs. Additionally, a new CC3-OH POC derivative with scrambled hydroxides exhibits a twofold increase in CO 2 adsorption capacity, attributed to enhanced interactions between hydroxide linkers and CO 2 . Furthermore, we explore the stability of azobenzene-containing organic cages formed via imine and amine bonds, revealing that the flexible amine bond allows for more efficient E-Z isomerization. Our findings highlight the transformative potential of PLs and azobenzene-derived systems in gas separation technologies, paving the way for innovative low-energy regeneration pathways.

36 MATERIALS SCIENCE↗

Bench-Scale Development of Promoted High-Capacity Structured Sorbents (Final Technical Report)

The project objective was to develop high-capacity structured sorbent capable of achieving low CO 2 removal from air. The sorbent framework consists of an amine-functionalized onto hydrophobic polymer backbone with an added promoter. The functionalized amine provides high CO 2 capacity and adsorption rates and the polymer backbone to reduce water uptake. For the sorbent development, multiple functionalized amines and promoters were assessed to select a candidate that achieved high CO 2 capacity, high adsorption rate, and high stability. A sorbent-coated filter design was selected as the structured sorbent, which provides high sorbent loading capacity and contains an electrically conductive nonwoven filter substrate that can be Joule-heated to provide efficient utilization of available electricity for sorbent regeneration. A commercial partner operated a pilot filter manufacturing line to produce the filter panels coated with the developed sorbent. A 1 kg CO 2 /day bench unit was designed and fabricated to test the structured filter sorbent. The key achievements from the structured sorbent development activity were demonstrating that existing filter industrial-scale processes can be used for manufacturing Susteon’s structured sorbent and completing a proof-of-concept demonstration of the commercially manufactured structured sorbent filters for CO 2 capture from air with direct, Joule-heated regeneration. A techno-economic assessment with sensitivity analysis was conducted on a 100,000 TPY facility with 85% operating capacity. Through sorbent optimization and process design improvements, it is estimated that the cost of capture was reduced from $\$$349/tCO 2 to $\$$241/tCO 2 . The TEA projects further reductions to $165/tCO 2 through enhancements in CO 2 adsorption rate and sorbent capacity and reducing manufacturing and scale up risks. A life cycle analysis was conducted on the same 100,000 TPY facility and confirmed that the facility’s electricity demand drives its greenhouse gas impact. It was determined that electricity supplied through the current grid mix would result in net-positive CO 2 emissions and that achieving net-negative emissions is only possible by powering the system with renewable electricity or fossil fuel sources equipped with carbon capture and sequestration.

36 MATERIALS SCIENCE↗

Multiple new-particle growth pathways observed at the US DOE Southern Great Plains field site

Abstract. New-particle formation (NPF) is a significant source of aerosol particles into the atmosphere. However, these particles are initially too small to have climatic importance and must grow, primarily through net uptake of low-volatility species, from diameters ∼ 1 to 30–100 nm in order to potentially impact climate. There are currently uncertainties in the physical and chemical processes associated with the growth of these freshly formed particles that lead to uncertainties in aerosol-climate modeling. Four main pathways for new-particle growth have been identified: condensation of sulfuric-acid vapor (and associated bases when available), condensation of organic vapors, uptake of organic acids through acid–base chemistry in the particle phase, and accretion of organic molecules in the particle phase to create a lower-volatility compound that then contributes to the aerosol mass. The relative importance of each pathway is uncertain and is the focus of this work. The 2013 New Particle Formation Study (NPFS) measurement campaign took place at the DOE Southern Great Plains (SGP) facility in Lamont, Oklahoma, during spring 2013. Measured gas- and particle-phase compositions during these new-particle growth events suggest three distinct growth pathways: (1) growth by primarily organics, (2) growth by primarily sulfuric acid and ammonia, and (3) growth by primarily sulfuric acid and associated bases and organics. To supplement the measurements, we used the particle growth model MABNAG (Model for Acid–Base chemistry in NAnoparticle Growth) to gain further insight into the growth processes on these 3 days at SGP. MABNAG simulates growth from (1) sulfuric-acid condensation (and subsequent salt formation with ammonia or amines), (2) near-irreversible condensation from nonreactive extremely low-volatility organic compounds (ELVOCs), and (3) organic-acid condensation and subsequent salt formation with ammonia or amines. MABNAG is able to corroborate the observed differing growth pathways, while also predicting that ELVOCs contribute more to growth than organic salt formation. However, most MABNAG model simulations tend to underpredict the observed growth rates between 10 and 20 nm in diameter; this underprediction may come from neglecting the contributions to growth from semi-to-low-volatility species or accretion reactions. Our results suggest that in addition to sulfuric acid, ELVOCs are also very important for growth in this rural setting. We discuss the limitations of our study that arise from not accounting for semi- and low-volatility organics, as well as nitrogen-containing species beyond ammonia and amines in the model. Quantitatively understanding the overall budget, evolution, and thermodynamic properties of lower-volatility organics in the atmosphere will be essential for improving global aerosol models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A dynamic parameterization of sulfuric acid–dimethylamine nucleation and its application in three-dimensional modeling

Sulfuric acid (SA) is a governing gaseous precursor for atmospheric new particle formation (NPF), a major source of global ultrafine particles, in environments studied around the world. In polluted urban atmospheres with high condensation sinks (CSs), the formation of stable SA–amine clusters, such as SA–dimethylamine (DMA) clusters, usually initializes intense NPF events. Coagulation scavenging and cluster evaporation are dominant sink processes of SA–amine clusters in urban atmospheres, yet these loss processes are not quantitatively included in the present parameterizations of SA–amine nucleation. We herein report a parameterization of SA–DMA nucleation, based on cluster dynamic simulations and quantum chemistry calculations, with certain simplifications to greatly reduce the computational costs. Compared with previous SA–DMA nucleation parameterizations, this new parameterization was able to reproduce the dependences of particle formation rates on temperature and CSs. We then incorporated it in a three-dimensional (3-D) chemical transport model to simulate the evolution of the particle number size distributions. Simulation results showed good consistency with the observations in the occurrence of NPF events and particle number size distributions in wintertime Beijing and represented a significant improvement compared to that using a parameterization without coagulation scavenging. Quantitative analysis shows that SA–DMA nucleation contributes significantly to nucleation rates and aerosol population during the 3-D simulations in Beijing (>99 % and >60 %, respectively). These results broaden the understanding of NPF in urban atmospheres and stress the necessity of including the effects of coagulation scavenging and cluster stability in simulating SA–DMA nucleation in 3-D simulations. Representing these processes is thus likely to improve model performance in particle source apportionment and quantification of aerosol effects on air quality, human health, and climate.

Li, Yuyang↗

Polyimidazopyrrolone model compounds.

The model reactions between phthalic anhydride and o-phenylenediamine were studied under conditions analogous to the polymerization and post-cyclization of dianhydrides with bis(o-diamines) to form polyimidazopyrrolones (Pyrrones). The route from the initial amide-acid-amine to the tetracyclic Pyrrone model when the reactions are conducted in aprotic solvents is highly competitive between isolatable benzimidazole-acid and imide-amine intermediates. Solid-state thermal conversion of the amide-acid-amine affords a unique dimeric species containing amide, imide, and benzimidazole functions. It was confirmed that melt techniques lead to disproportionation products. The application of these findings to related polymer synthesis is discussed.

Young, P. R.↗

Effects of multifunctional crosslinking agents on the thermomechanical properties of polyimide films

Three polyfunctional amines were synthesized. Polyimide films containing varying amounts of the amine crosslinking agents were prepared. Their thermomechanical properties were compared with those of control film samples prepared from difunctional amines. The effect of crosslink density on isothermal weight loss, polymer softening, and glass transition temperature is discussed.

Delvigs, P.↗

Effects of multifunctional crosslinking agents on the thermomechanical properties of polyimide films

The potential of high temperature resistant polymers such as polyimides (PI) and polyphenylquinoxalines (PPQ) as matrix resins in fiber-reinforced composites has not been fully realized to date. One of the problems associated with these resins is that they exhibit creep, or thermoplastic yielding under load at temperatures approaching 316 C (600 F). The purpose of this investigation was to further reduce thermoplastic behavior of polyimide resins by substituting a controlled amount of the diamine monomer with crosslinking agents having a higher amine functionality. The knowledge gained from a study of the thermomechanical properties of the crosslinked resins would then be used in the fabrication of fiber-reinforced polyimide composites. This report describes the synthesis and characterization of three new polyfunctional amines. Polyimide films containing varying amounts of the cross-linking agents were prepared, and their properties compared with those of control samples prepared with difunctional amines. The effect of crosslink density on isothermal weight loss, polymer softening, and glass transition temperatures is discussed.

Delvigs, P.↗

Monomers for thermosetting and toughening epoxy resins

Eight glycidyl amines were prepared by alkylating the parent amine with epichlorohydrin to form chlorohydrin, followed by cyclization with aqueous NaOH. Three of these compounds contained propargyl groups with postcuring studies. A procedure for quantitatively estimating the epoxy content of these glycidyl amines was employed for purity determination. Two diamond carbonates and several model propargly compounds were prepared. The synthesis of three new diamines, two which contain propargyloxy groups, and another with a sec-butyl group is in progress. These materials are at the dinitro stage ready for the final hydrogenation step. Four aromatic diamines were synthesized for mutagenic testing purposes. One of these compounds rapidly decomposes on exposure to air.

Pratt, J. R.↗

Imide modified epoxy matrix resins

Results of a program designed to develop tough imide modified epoxy (IME) resins cured by bisimide amine (BIA) hardeners are presented. State of the art epoxy resin, MY720, was used. Three aromatic bisimide amines and one aromatic aliphatic BIA were evaluated. BIA's derived from 6F anhydride (3,3 prime 4,4 prime-(hexafluoro isopropyl idene) bis (phthalic anhydride) and diamines, 3,3 prime-diam nodiphenyl sulfone (3,3 prime-DDS), 4,4 prime-diamino diphenyl sulfone (4,4 prime-DDS), 1.12-dodecane diamine (1,12-DDA) were used. BIA's were abbreviated 6F-3,3 prime-DDS, 6F-4,4 prime-DDS, 6F-3,3 prime-DDS-4,4 prime DDS, and 6F-3,3 prime-DDS-1,12-DDA corresponding to 6F anhydride and diamines mentioned. Epoxy resin and BIA's (MY720/6F-3,3 prime-DDS, MY720/6F-3,3 prime-DDS-4,4 prime-DDS, MY720/6F-3,3 prime-DDS-1,12-DDA and a 50:50 mixture of a BIA and parent diamine, MY720/6F-3,3 prime-DDS/3,3 prime-DDS, MY720/6F-3,3 prime-DDS-4,4 prime-DDS/3,3 prime-DDS, MY720/6F-3,3 prime-DDS-1,12-DDA/3,3 prime-DDS were studied to determine effect of structure and composition. Effect of the addition of two commercial epoxies, glyamine 200 and glyamine 100 on the properties of several formulations was evaluated. Bisimide amine cured epoxies were designated IME's (imide modified epoxy). Physical, thermal and mechanical properties of these resins were determined. Moisture absorption in boiling water exhibited by several of the IME's was considerably lower than the state of the art epoxies (from 3.2% for the control and state of the art to 2.0 wt% moisture absorption). Char yields are increased from 20% for control and state of the art epoxies to 40% for IME resins. Relative toughness characteristics of IME resins were measured by 10 deg off axis tensile tests of Celion 6000/IME composites. Results show that IME's containing 6F-3,3 prime-DDS or 6F-3,3 prime-DDS-1,12-DDA improved the "toughness" characteristics of composites by about 35% (tensile strength), about 35% (intralaminar shear strength), and about 78% (shear strain to failure) relative to the control composite.

Scola, D. A.↗

Synthesis of N-Substituted Silaneamines: Monomeric Precursors of Silicon Carbide-Nitride Fibers

Silanetriamines are prepared by the condensation of methyl or phenyl trichlorosilane with a primary amine. The amines used were methyl, n-propyl, n-butyl and allyl. The silaneamines were prepared by adding the chlorosilane to a solution of the amine in either petroleum ether or toluene. The compounds were purified by distillation and characterized by infrared and nuclear magnetic resonance spectroscopy.

Crouse, D. J.↗

Toughening of BIS maleimide resins: Synthesis and characterization of maleimide terminated poly(arylene ether) oligomers and polymers

Amine functional poly(arylene ether) sulfones were previously reported. Herein, the chemistry was extended to amorphous poly(arylene ether) ketones because of their higher fracture toughness values, relative to the polysulfones. It was demonstrated that the amino functional oligomers undergo a self-crosslinking reaction at temperatures above about 220 C. This produces an insoluble, but ductile network that has excellent resistance. A ketamine structure hypothesis was proposed and verified using solid state magic angle NMR. In most cases, the water generated upon ketamine formation is too low to produce porosity and solid networks are obtained. The stability of the ketamine networks towards hydrolysis is excellent. The chemistry was further demonstrated to be able to crosslink preformed nonfunctional poly(arylene ether) ketones if a difunctional amine was utilized. This concept has the possibility of greatly improving the creep resistance of thermoplastics. Also, a new technique was developed for converting the amine functional oligomers cleanly into maleimide structures. This method involves reacting maleic anhydride with monomeric aminophenols in the presence of solvent mixtures.

Mcgrath, J. E.↗

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.↗

Fluorescence Studies of Protein Crystallization Interactions

We are investigating protein-protein interactions in under- and over-saturated crystallization solution conditions using fluorescence methods. The use of fluorescence requires fluorescent derivatives where the probe does not markedly affect the crystal packing. A number of chicken egg white lysozyme (CEWL) derivatives have been prepared, with the probes covalently attached to one of two different sites on the protein molecule; the side chain carboxyl of ASP 101, within the active site cleft, and the N-terminal amine. The ASP 101 derivatives crystallize while the N-terminal amine derivatives do not. However, the N-terminal amine is part of the contact region between adjacent 43 helix chains, and blocking this site does would not interfere with formation of these structures in solution. Preliminary FRET data have been obtained at pH 4.6, 0.1M NaAc buffer, at 5 and 7% NaCl, 4 C, using the N-terminal bound pyrene acetic acid (PAA, Ex 340 nm, Em 376 nm) and ASP 101 bound Lucifer Yellow (LY, Ex 425 nm, Em 525 nm) probe combination. The corresponding Csat values are 0.471 and 0.362 mg/ml (approximately 3.3 and approximately 2.5 x 10 (exp 5) M respectively), and all experiments were carried out at approximately Csat or lower total protein concentration. The data at both salt concentrations show a consistent trend of decreasing fluorescence yield of the donor species (PAA) with increasing total protein concentration. This decrease is apparently more pronounced at 7% NaCl, consistent with the expected increased intermolecular interactions at higher salt concentrations (reflected in the lower solubility). The estimated average distance between protein molecules at 5 x 10 (exp 6) M is approximately 70 nm, well beyond the range where any FRET can be expected. The calculated RO, where 50% of the donor energy is transferred to the acceptor, for the PAA-CEWL * LY-CEWL system is 3.28 nm, based upon a PAA-CEWL quantum efficiency of 0.41.

Pusey, Marc L.↗

Strained Hydrocarbons as Potential Hypergolic Fuels

A storable combination of high-energy hypergolic fuel and oxidizer is advantageous to the future of reusable launch vehicles (RLVs). The combination will allow an increase in energy per unit volume of fuel and eliminate the need for an external ignition system. Strained systems have been studied as potential high-density fuels. Adding hypergolic functional groups, such as amino groups, to these hydrocarbons will potentially allow auto ignition of strained systems with hydrogen peroxide. Several straight chain amines and their strained counterparts containing an equivalent number of carbon atoms have been purchased and synthesized. These amines provide initial studies to determine the effects of fuel vapor pressure, strain energy, fuel miscibility, and amine substitution upon fuel ignition time and hypergolicity with hydrogen peroxide as an oxidizer.

Source record↗

Recent Selected Ion Flow Tube (SIFT) Studies Concerning the Formation of Amino Acids in the Gas Phase

Recently the simplest amino acid, glycine, has been detected in interstellar clouds, ISC, although this has since been contested. In order to substantiate either of these claims, plausible routes to amino acids need to be investigated. For gas phase synthesis, the SIFT technique has been employed to study simple amino acids via ion-molecule reactions of several ions of interstellar interest with methylamine, ethylamine, formic acid, acetic acid, and methyl formate. Carboxylic acid type ions were considered in the reactions involving the amines. In reactions where the carboxylic acid and methyl formate neutrals were studied, the reactant ions were primarily amine ion fragments. It was observed that the amines and acids preferentially fragment or accept a proton whenever energetically possible. NH3(+), however, uniquely reacted with the neutrals via atom abstraction to form NH4(+). These studies yielded a body of data relevant to astrochemistry, supplementing the available literature. However, the search for gas phase routes to amino acids using conventional molecules has been frustrated. Our most recent research investigates the fragmentation patterns of several amino acids and several possible routes have been suggested for future study.

Jackson, Douglas M.↗