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The present invention relates to cross-linked polyolefin aerogels in simple and fiber-reinforced composite form. Of particular interest are polybutadiene aerogels. Especially aerogels derived from polybutadienes functionalized with anhydrides, amines, hydroxyls, thiols, epoxies, isocyanates or combinations thereof.
Intravenous injections of the indirect sympathetic amine, tyramine, are used as a test of peripheral adrenergic function. The authors measured the time course of increases in ejection fraction, heart rate, systolic and diastolic pressure, popliteal artery flow, and greater saphenous vein diameter before and after an injection of 4.0 mg/m(2) body surface area of tyramine in normal human subjects. The tyramine caused moderate, significant increases in systolic pressure and significant decreases in total peripheral resistance. The earliest changes were a 30% increase in ejection fraction and a 16% increase in systolic pressure, followed by a 60% increase in popliteal artery flow and a later 11% increase in greater saphenous vein diameter. There were no changes in diastolic pressure or heart rate. These results suggest that pressor responses during tyramine injections are primarily due to an inotropic response that increases cardiac output and pressure and causes a reflex decrease in vascular resistance. Thus, tyramine pressor tests are a measure of cardiac, but not vascular, sympathetic function.
A number of amine-based carbon dioxide (CO2) removal systems have been developed for atmosphere revitalization in closed loop life support systems. Most recently, Hamilton Sundstrand developed an amine-based sorbent, designated SA9T, possessing approximately 2-fold greater capacity compared to previous formulations. This new formulation has demonstrated applicability for controlling CO2 levels within vehicles and habitats as well as during extravehicular activity (EVA). System volume is competitive with existing technologies. Further enhancements in system performance can be realized by incorporating humidity and trace contaminant control functions within an amine-based atmosphere revitalization system. A 3-year effort to develop prototype hardware capable of removing CO2, H2O, and trace contaminants from a cabin atmosphere has been initiated. Progress pertaining to defining system requirements and identifying alternative amine formulations and substrates is presented.
Polyimide aerogels with three-dimensional cross-linked structure are made using linear oligomeric segments of polyimide, and linked with one of the following into a 3D structure: trifunctional aliphatic or aromatic amines, latent reactive end caps such as nadic anhydride or phenylethynylphenyl amine, and silica or silsesquioxane cage structures decorated with amine. Drying the gels supercritically maintains the solid structure of the gel, creating a polyimide aerogel with improved mechanical properties over linear polyimide aerogels. Lightweight, low-density structures are desired for acoustic and thermal insulation for aerospace structures, habitats, astronaut equipment, and aeronautic applications. Aerogels are a unique material for providing such properties because of their extremely low density and small pore sizes. However, plain silica aerogels are brittle. Reinforcing the aerogel structure with a polymer (X-Aerogel) provides vast improvements in strength while maintaining low density and pore structure. However, degradation of polymers used in cross-linking tends to limit use temperatures to below 150 C. Organic aerogels made from linear polyimide have been demonstrated, but gels shrink substantially during supercritical fluid extraction and may have lower use temperature due to lower glass transition temperatures. The purpose of this innovation is to raise the glass transition temperature of all organic polyimide aerogel by use of tri-, tetra-, or poly-functional units in the structure to create a 3D covalently bonded network. Such cross-linked polyimides typically have higher glass transition temperatures in excess of 300 400 C. In addition, the reinforcement provided by a 3D network should improve mechanical stability, and prevent shrinkage on supercritical fluid extraction. The use of tri-functional aromatic or aliphatic amine groups in the polyimide backbone will provide such a 3D structure.
We report on the synthesis and characterization of a novel series low-molar-mass ether-imide rod-shaped model compounds. All ether-imides were obtained by terminating the appropriate rigid core dianhydride, i.e. pyromellitic dianhydride (PMDA), 1,4,5,8-naphthalenetetracarboxylic dianhydride (NDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), and 3,3,4,4'-oxydiphthalic dianhydride (ODPA) with three flexible aryl-ether tails of different chain length. The mono-functional aryl-ether amines, i.e. 4-(3-phenoxy-phenoxy)-phenylamine (2) and 4-(3-phenoxy-3-phenoxy-phenoxy)-phenylamine (4), were synthesized using standard fluoro-displacement and Ullmann condensation techniques. The corresponding ether-imide model compounds were obtained in high yields using a one-step solution imidization procedure. Increasing the number of meta-substituted aryl-ether units reduces the melt transition temperatures and at the same time it increases the solubility of the model compounds. Most model compounds are crystalline solids and form isotropic melts upon heating. 2,7-Bis-(-4-phenoxy-phenyl)-benzo[Imn][3,8]phenanthroline1,3,6,8-tetraone (NDA-n0), however, displays a smectic A (SA) when cooled from the isotropic phase, followed by what appears to be either a highly ordered smectic phase or a, columnar phase. This is the first example, known to date, in which a mesophase is detected in a wholly aromatic ether-imide compound. For all compounds we present spectroscopic data and X-ray diffraction data. Cyclic voltammetry was used to determine the redox behavior and pertinent energy levels of the model compounds.
A proposal to study the function of the adrenal gland in the rat during stress is presented. In the proposed project, three different phases of experimentation will be undertaken. The first phase includes establishment of the circadian rhythm of both brain amines and glucocoticoids, under normal conditions and under chronic and acute stressful conditions. The second phase includes the study of the pharmacokinetics of glucocorticoid binding under normal and stress conditions. The third phase includes brain uptake and binding under different experimental conditions. In the outlined experiments brain biogenic amines will be evaluated, adrenal functions will be measured and stress effect on those parameters will be studied. It is hoped that this investigation can explain some of the complex relationships between the brain neurotransmitter and adrenal function.
A regenerable solid amine material to perform the functions of humidity control and CO2 removal for space shuttle type vehicle is reported. Both small scale and large scale testing have shown this material to be competitive, especially for the longer shuttle missions. However, it had been observed that the material off-gasses ammonia under certain conditions. This presents two concerns. The first, that the ammonia would contaminate the cabin atmosphere, and second, that the material is degrading with time. An extensive test program has shown HS-C to produce only trace quantities of atmospheric contaminants, and under normal extremes, to have no practical life limitation.
Under a cooperative agreement with NASA, Hamilton Sundstrand has successfully designed, fabricated, tested and delivered three, state-of-the-art, solid amine prototype systems capable of continuous CO2 and humidity removal from a closed, habitable atmosphere. Two prototype systems (CAMRAS #1 and #2) incorporated a linear spool valve design for process flow control through the sorbent beds, with the third system (CAMRAS #3) employing a rotary valve assembly that improves system fluid interfaces and regeneration capabilities. The operational performance of CAMRAS #1 and #2 has been validated in a relevant environment, through both simulated human metabolic loads in a closed chamber and through human subject testing in a closed environment. Performance testing at Hamilton Sundstrand on CAMRAS #3, which incorporates a new valve and modified canister design, showed similar CO2 and humidity removal performance as CAMRAS #1 and #2, demonstrating that the system form can be modified within certain bounds with little to no effect in system function or performance. Demonstration of solid amine based CO2 and humidity control is an important milestone in developing this technology for human spaceflight. The systems have low power requirements; with power for air flow and periodic valve actuation and indication the sole requirements. Each system occupies the same space as roughly four shuttle non-regenerative LiOH canisters, but have essentially indefinite CO2 removal endurance provided a regeneration pathway is available. Using the solid amine based systems to control cabin humidity also eliminates the latent heat burden on cabin thermal control systems and the need for gas/liquid phase separation in a low gravity environment, resulting in additional simplification of vehicle environmental control and life support system process requirements.
The toughness and coefficient of thermal expansion of a series of functionalized graphene sheet - epoxy nanocomposites are investigated. Functionalized graphene sheets are produced by splitting graphite oxide into single graphene sheets through a rapid thermal expansion process. These graphene sheets contain approx. 10% oxygen due to the presence of hydroxide, epoxide, and carboxyl functional groups which assist in chemical bond formation with the epoxy matrix. Intrinsic surface functionality is used to graft alkyl amine chains on the graphene sheets, and the addition of excess hardener insures covalent bonding between the epoxide matrix and graphene sheets. Considerable improvement in the epoxy dimensional stability is obtained. An increase in nanocomposite toughness is observed in some cases.
Metal oxide containing polymers and particularly styrene, acrylic or protein polymers containing fine, magnetic iron oxide particles are formed by combining a NO.sub.2 -substituted polymer with an acid such as hydrochloric acid in the presence of metal, particularly iron particles. The iron is oxidized to fine, black Fe.sub.3 O.sub.4 particles which deposit selectively on the polymer particles. Nitrated polymers are formed by reacting functionally substituted, nitrated organic compounds such as trinitrobenzene sulfonate or dinitrofluoro benzene with a functionally coreactive polymer such as an amine modified acrylic polymer or a protein. Other transition metals such as cobalt can also be incorporated into polymers using this method.
An ablative foam composition is formed of approximately 150 to 250 parts by weight polymeric isocyanate having an isocyanate functionality of 2.6 to 3.2; approximately 15 to 30 parts by weight reactive flame retardant having a hydroxyl number range from 200-260; approximately 10 to 40 parts by weight non-reactive flame retardant; approximately 10 to 40 parts by weight nonhydrolyzable silicone copolymer having a hydroxyl number range from 75-205; and approximately 3 to 16 parts by weight amine initiated polyether resin having an isocyanate functionality greater than or equal to 3.0 and a hydroxyl number range from 400-800.
Carbon dioxide (CO2) and humidity control is a key function of the spacesuit Portable Life Support Subsystem (PLSS). The latest spacesuit design utilizes a pressure swing bed containing a solid amine sorbent to scrub CO2 and humidity produced by the crewmember from the ventilation loop. The solid amine sorbent removes CO2 and humidity from the ventilation loop through a chemisorption mechanism. Simultaneously, CO2 and humidity are desorbed to vacuum via the two-bed pressure swing system during operation. This continuous regeneration allows for longer Extravehicular Activity (EVA) times while minimizing maintenance, consumables, and power usage. This concept has been in development for over 20 years, during which many prototypes and design iterations have been fabricated and evaluated. This paper discusses the recent Rapid Cycle Amine (RCA) design, development, and testing that has been done to advance the technology. The most recent fabrication is the RCA 3.0. It was delivered to NASA Johnson Space Center in 2015 and has since been tested at the component level and at the integrated PLSS level. The purpose of the component level testing was to understand CO2 removal capacity, end-of-life performance, and establish a baseline performance prior to integrated testing. The RCA 3.0 was integrated into the Exploration Extravehicular Mobility Unit (xEMU) PLSS for a comprehensive Design Verification Test (DVT) series. The integrated testing provided the benefit of characterizing the impact performance degradation has on the system. Many of the RCA requirements were developed through analysis, based on the limitations of the PLSS and, in some cases, assumptions about the system and flow behavior. Integrated testing was an opportunity to validate those requirements and assumptions. While the RCA 3.0 was being tested, the next design iteration, RCA 4.0, was under development. The RCA 4.0 preliminary design phase began in late-2019 and shortly after the Preliminary Design Review, the critical design phase began in 2021. The design work has concluded with the completion of a Pre-Manufacturing Review in 2022. This paper provides an overview of the RCA 4.0 system design, summarizes the results of integrated RCA 3.0 testing, and discusses the pertinence of driving requirements such as mass, volume, and power consumption.
A regenerable, three man preprototype solid amine, water desorbed (SAWD) CO2 removal and concentation subsystem was designed, fabricated, and successfully acceptance tested by Hamilton Standard. The preprototype SAWD incorporates a single solid amine canister to perform the CO2 removal function, an accumulator to provide the CO2 storage and delivery function, and a microprocessor which automatically controls the subsystem sequential operation and performance. The SAWD subsystem was configured to have a CO2 removal and CO2 delivery capability at the rate of 0.12 kg/hr (0.264 lb/hr) over the relative humidity range of 35 to 70%. The controller was developed to provide fully automatic control over the relative humidity range via custom software that was generated specifically for the SAWD subsystem. The preprototype SAWD subsystem demonstrated a total of 281 hours (208) cycles of operation during ten acceptance tests that were conducted over the 3 to 70% relative humidity range. This operation was comprised of 178 hours (128 cycles) in the CO2 overboard mode and 103 hours (80 cycles) in the CO2 reduction mode. The average CO2 removal/delivery rate met or exceeded the design specification rate of 0.12 kg/hr (0.254 lb/hr) for all ten of the acceptance tests.
Post fertilization growth of tobacco ovary tissues treated with inhibitors of polyamine (PA) biosynthesis was examined in relation to endogenous PA titers and the activities of arginine decarboxylase (ADC, EC 4.1.1.19) and ornithine decarboxylase (ODC, EC 4.1.1.17). DL-alpha-Difluoromethylornithine (DFMO) and DL-alpha-difluoromethylarginine (DFMA), specific, irreversible ("suicide") inhibitors of ODC and ADC in vitro, were used to modulate PA biosynthesis in excised flowers. ODC represented >99% of the total decarboxylase activity in tobacco ovaries. In vivo inhibition of ODC with DFMO resulted in a significant decrease in PA titers, ovary fresh weight and protein content. Simultaneous inhibition of both decarboxylases by DFMO and DFMA produced only a marginally greater depression in growth and PA titers, indicating that ODC activity is rate-limiting for PA biosynthesis in these tissues. Paradoxically, DFMA alone inhibited PA biosynthesis, not as a result of a specific inhibition of ADC, but primarily through the inactivation of ODC. In vivo inhibition of ODC by DFMA appears to result from arginase-mediated hydrolysis of this inhibitor to urea and DFMO, the suicide substrate for ODC. Putrescine conjugates in tobacco appear to function as a storage form of this amine which, upon hydrolysis, may contribute to Put homeostasis during growth.
Nano-engineered materials are multi-functional materials with superior mechanical, thermal and electrical properties. Nanomaterials may be used for a variety of space exploration applications, including ultracapacitors, active/passive thermal management materials, and nanofiltration for water recovery. Additional applications include electrical power/energy storage systems, hybrid systems power generation, advanced proton exchange membrane fuel cells, and air revitalization. The need for nanomaterials and their growth, characterization, processing and space exploration applications is discussed. Data is presented for developing solid-supported amine adsorbents based on carbon nanotube materials and functionalization of nanomaterials is examined.
Transient hypercapnic hyperoxemia was induced in two Rett syndrome children by the administration of a gaseous mixture of 80 percent O2 and 20 percent CO2. Time course studies of neurotransmitters and their metabolites showed an immediate and marked increase in central biogenic amine turnover following inhalation of the gas mixture. The increased turnover of biogenic amines was associated with improved clinical changes. This suggests a coupled relationship and provides further support for an etiological role of neurotransmitter dysfunction in Rett syndrome. In a complementary study, elevation of pulmonary CO2 by application of a simple rebreathing device resulted in improvement of abnormal blood gases and elimination of the Cheyne-Stokes-like respiratory pattern of the Rett syndrome. Near normalization of the EEG occurred when a normal respiratory pattern was imposed by means of a respirator. Taken together, these results lead to the preliminary conclusion that cerebral hypoxemia secondary to abnormal respiratory function may contribute to diminished production of biogenic amines in Rett syndrome.
The NASA Stardust mission successfully collected material from Comet 81P/Wild 2 [1], including authentic cometary grains [2]. X-ray absorption near-edge structure (XANES) spectroscopy analysis of these samples indicates the presence of oxygen-rich and nitrogen-rich organic materials, which contain a broad variety of functional groups (carbonyls, C=C bonds, aliphatic chains, amines, arnides, etc.) [3]. One component of these organics appears to contain very little aromatic carbon and bears some similarity to the organic residues produced by the irradiation of ices of interstellar/cometary composition, Stardust samples were also recently shown to contain glycine, the smallest biological amino acid [4]. Organic residues produced froth the UV irradiation of astrophysical ice analogs are already known to contain a large suite of organic molecules including amino acids [5-7], amphiphilic compounds (fatty acids) [8], and other complex species. This work presents a comparison between XANES spectra measured from organic residues formed in the laboratory with similar data of cometary samples collected by the Stardust mission
Organic material found in meteorites and interplanetary dust particles is enriched in D and N-15. This is consistent with the idea that the functional groups carrying these isotopic anomalies, nitriles and amines, were formed by ion-molecule chemistry in the protosolar nebula, Theoretical models of interstellar fractionation at low temperatures predict large enrichments in both D and N-15 and can account for the largest isotopic enrichments measured in carbonaceous meteorites. However, more recent measurements have shown that, in some primitive samples, a large N-15 enrichment does not correlate with one in D, and that some D-enriched primitive material displays little, if any, N-15 enrichment. By considering the spin-state dependence in ion-molecule reactions involving the ortho and para forms of H2, we show that ammonia and related molecules can exhibit such a wide range of fractionation for both N-15 and D in dense cloud cores. We also show that while the nitriles, HCN and HNC, contain the greatest N=15 enrichment, this is not expected to correlate with extreme D enrichment. These calculations therefore support the view that solar system N-15 and D isotopic anomalies have an interstellar heritage. We also compare our results to existing astronomical observations and briefly discuss future tests of this model.