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At least 73 records · Page 4

Early immune response and regulation of IL-2 receptor subunits

Affymetrix oligonucleotide arrays were used to monitor expression of 8796 genes and probe sets in activated T-cells; analysis revealed that 217 genes were significantly upregulated within 4 h. Induced genes included transcription factors, cytokines and their receptor genes. Analysis by semi-quantitative RT-PCR confirmed the significant induction of IL-2, IL-2R(gamma) and IL-2R(alpha). Forty-eight of the 217 induced genes are known to or predicted to be regulated by a CRE promoter/enhancer. We found that T-cell activation caused a significant increase in CREB phosphorylation furthermore, inhibition of the PKC pathway by GF109203 reduced CREB activation by 50% and inhibition of the PKA pathway caused a total block of CREB phosphorylation and significantly reduced IFN(gamma), IL-2 and IL-2R(alpha) gene expression by approximately 40% (p<0.001). PKC(theta) plays a major role in T-cell activation: inhibition of PKC significantly reduced the expression of IFN(gamma), IL-2 and IL-2R(alpha). Since PKC blocked activation of CREB, we studied potential cross-talk between the PKC and the PKA/MAPK pathways, PMA-stimulated Jurkat cells were studied with specific signal pathway inhibitors. Extracellular signal-regulated kinase-2 (ERK2) pathway was found to be significantly activated greater than seven-fold within 30 min; however, there was little activation of ERK-1 and no activation of JNK or p38 MAPK. Inhibition of the PKA pathway, but not the PKC pathway, resulted in inhibition of ERK1/2 activation at all time points, inhibition of MEK1 and 2 significantly blocked expression of IL-2 and IL-2R(alpha). Gene expression of IL-2R(alpha) and IFN(gamma) was dependent on PKA in S49 wt cells but not in kin- mutants. Using gel shift analysis, we found that forskolin activation of T-cells resulted in activation of AP1 sites; this increase in nuclear extract AP1 was significantly blocked by MEK1 inhibitor U0126. Taken together, these results suggest that the PKA in addition to PKC and MAPK pathways plays a role in early T-cell activation and induction of IL-2, IL-2R(alpha) and IFN(gamma) gene expression.

Non-NASA Center↗

Mechanisms of Hysteresis and Reversibility across the Voltage-Driven Perovskite–Brownmillerite Transformation in Electrolyte-Gated Ultrathin La 0.5 Sr 0.5 CoO 3−δ

Perovskite cobaltites have emerged as archetypes for electrochemical control of materials properties in electrolyte-gate devices. Voltage-driven redox cycling can be performed between fully oxygenated perovskite and oxygen-vacancy-ordered brownmillerite phases, enabling exceptional modulation of the crystal structure, electronic transport, thermal transport, magnetism, and optical properties. The vast majority of studies, however, have focused heavily on the perovskite and brownmillerite end points. In contrast, here we focus on hysteresis and reversibility across the entire perovskite ↔ brownmillerite topotactic transformation, combining gate-voltage hysteresis loops, minor hysteresis loops, quantitative operando synchrotron X-ray diffraction, and temperature-dependent (magneto)transport, on ion-gel-gated ultrathin (10-unit-cell) epitaxial La 0.5 Sr 0.5 CoO 3-δ films. Further, gate-voltage hysteresis loops combined with operando diffraction reveal a wealth of new mechanistic findings, including asymmetric redox kinetics due to differing oxygen diffusivities in the two phases, nonmonotonic transformation rates due to the first-order nature of the transformation, and limits on reversibility due to first-cycle structural degradation. Minor loops additionally enable the first rational design of an optimal gate-voltage cycle. Combining this knowledge, we demonstrate state-of-the-art nonvolatile cycling of electronic and magnetic properties, encompassing >10 5 transport ON/OFF ratios at room temperature, and reversible metal-insulator-metal and ferromagnet-nonferromagnet-ferromagnet cycling, all at 10-unit-cell thickness with high room-temperature stability. This paves the way for future work to establish the ultimate cycling frequency and endurance of such devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

$In-situ$ synchrotron x-ray diffraction and thermal expansion of TiB2 up to ~3050 °C

There is an increasing interest in understanding the performance and properties of ultra-high temperature ceramics due to their high melting points (<3000 °C) that make them promising for extreme environment applications. In-situ high temperature X-ray diffraction experiments were performed on TiB 2 beads up to ~3050 °C. For these experiments, TiB 2 powders were fabricated into spherical beads via gel casting methods and densified in a high temperature graphite furnace. These sample beads were then levitated in a conical nozzle levitator with reducing atmosphere (3% H 2 -Ar) while being heated using a 400 W CO 2 laser. During levitation a collimated synchrotron X-ray source was used to perform in-situ, temperature-dependent structural characterizations. The anisotropic coefficients of thermal expansion of TiB 2 were characterized as a function of temperature up to ~3050 °C. Elucidation of these properties are critical for the advancement of TiB 2 ceramics and other transition metal di-borides for use in high temperature applications such as hypersonic platforms, nuclear reactors, and atmospheric re-entry.

36 MATERIALS SCIENCE↗

Preparative cell electrophoresis at 1 and 0 gravity

It is attempted to show that the use of heavy water (D2O) as starting cushion for the cells combines the advantages of the required density difference, with no lasting biochemical or physiochemical influence on the cells. Phosphate buffers of low ionic strength were prepared in distilled water or heavy water. A vertical starch gel electrophoresis was used to support a cylindrical polystyrene electrophoresis tube used for lymphocyte separations, 25 cm in length and 0.75 cm I.D., prepared from a 10 ml disposable pipet. Erythrocyte separations were carried out in a jacketed rectangular plexiglas chamber. It is pointed out that the described preparative D2O gradient electrophoresis method cannot be readily used for the measurement of electrophoretic mobilities for analytical purposes. However, for the preparative separation of cells with only slightly different electrokinetic properties the method appears promising, simple, and entirely inocuous to the cells.

Van Oss, C. J.↗

Evaluation of Impinging Stream Vortex Chamber Concepts for Liquid Rocket Engine Applications

NASA Marshall Space Flight Center (MSFC) and the U. S. Army are jointly investigating vortex chamber concepts for cryogenic oxygen/hydrocarbon fuel rocket engine applications. One concept, the Impinging Stream Vortex Chamber Concept (ISVC), has been tested with gel propellants at AMCOM at Redstone Arsenal, Alabama. A version of this concept for the liquid oxygen (LOX)/hydrocarbon fuel (RP-1) propellant system is derived from the one for the gel propellant. An unlike impinging injector is employed to deliver the propellants to the chamber. MSFC has also designed two alternative injection schemes, called the chasing injectors, associated with this vortex chamber concept. In these injection techniques, both propellant jets and their impingement point are in the same chamber cross-sectional plane. One injector has a similar orifice size with the original unlike impinging injector. The second chasing injector has small injection orifices. The team has achieved their objectives of demonstrating the self-cooled chamber wall benefits of ISVC and of providing the test data for validating computational fluids dynamics (CFD) models. These models, in turn, will be used to design the optimum vortex chambers in the future.

Trinh, Huu↗

Preventing Ice Before it Forms

In the late 1990s, a team of engineers at Ames Research Center invented an anti-icing fluid to keep ice from building up on airplane wings. Ice on wings can be a serious safety hazard, especially during takeoff, when a sheet of ice the thickness of a compact disc can reduce lift by 25 percent or more. The typical approach to clearing off the ice is to use a deicing solution once the ice has built up. The fluid created by the Ames team, though, when applied to a dry surface, prevents the ice from even forming a surface bond, which saves deicing time and money, while also preventing excessive use of chemical solvents. If, however, the solution is not applied before ice forms, it also serves as a traditional deicing formula. The formula contains propylene glycol, which has a very low freezing point, and a thickener, which helps the fluid adhere to the surface. Ice gathers on top of the formula, and then it can be wiped off with little effort. This thickening agent, a pseudo-plastic, sprays on as a liquid, like lemonade, gels like a lemon sherbet, turns back to a liquid when wiped, and then gels again into its sherbet consistency when left to solidify. The sherbet-gel stage is especially important when the formula is sprayed onto a vertical or steeped surface, as it clings better than a liquid would.

Source record↗

Rapid Protein Separations in Microfluidic Devices

This paper describes fabrication of glass and plastic microfluidic devices for protein separations. Although the long-term goal is to develop a microfluidic device for two-dimensional gel electrophoresis, this paper focuses on the first dimension-isoelectric focusing (IEF). A laser-induced fluorescence (LIF) imaging system has been built for imaging an entire channel in an IEF device. The whole-channel imaging eliminates the need to migrate focused protein bands, which is required if a single-point detector is used. Using the devices and the imaging system, we are able to perform IEF separations of proteins within minutes rather than hours in traditional bench-top instruments.

MICROFLUIDICS↗

Purification and characterization of ornithine transcarbamylase from pea (Pisum sativum L.)

Pea (Pisum sativum) ornithine transcarbamylase (OTC) was purified to homogeneity from leaf homogenates in a single-step procedure, using delta-N-(phosphonacetyl)-L-ornithine-Sepharose 6B affinity chromatography. The 1581-fold purified OTC enzyme exhibited a specific activity of 139 micromoles citrulline per minute per milligram of protein at 37 degrees C, pH 8.5. Pea OTC represents approximately 0.05% of the total soluble protein in the leaf. The molecular weight of the native enzyme was approximately 108,200, as estimated by Sephacryl S-200 gel filtration chromatography. The purified protein ran as a single molecular weight band of 36,500 in sodium dodecyl sulfate-polyacrylamide gel electrophoresis. These results suggest that the pea OTC is a trimer of identical subunits. The overall amino acid composition of pea OTC is similar to that found in other eukaryotic and prokaryotic OTCs, but the number of arginine residues is approximately twofold higher. The increased number of arginine residues probably accounts for the observed isoelectric point of 7.6 for the pea enzyme, which is considerably more basic than isoelectric point values that have been reported for other OTCs.

Non-NASA Center↗

Characterization of auxin-binding proteins from zucchini plasma membrane

We have previously identified two auxin-binding polypeptides in plasma membrane (PM) preparations from zucchini (Cucurbita pepo L.) (Hicks et al. 1989, Proc. Natl. Acad. Sci. USA 86, 4948-4952). These polypeptides have molecular weights of 40 kDa and 42 kDa and label specifically with the photoaffinity auxin analog 5-N3-7-3H-IAA (azido-IAA). Azido-IAA permits both the covalent and radioactive tagging of auxin-binding proteins and has allowed us to characterize further the 40-kDa and 42-kDa polypeptides, including the nature of their attachment to the PM, their relationship to each other, and their potential function. The azido-IAA-labeled polypeptides remain in the pelleted membrane fraction following high-salt and detergent washes, which indicates a tight and possibly integral association with the PM. Two-dimensional electrophoresis of partially purified azido-IAA-labeled protein demonstrates that, in addition to the major isoforms of the 40-kDa and 42-kDa polypeptides, which possess isoelectric points (pIs) of 8.2 and 7.2, respectively, several less abundant isoforms that display unique pIs are apparent at both molecular masses. Tryptic and chymotryptic digestion of the auxin-binding proteins indicates that the 40-kDa and 42-kDa polypeptides are closely related or are modifications of the same polypeptide. Phase extraction with the nonionic detergent Triton X-114 results in partitioning of the azido-IAA-labeled polypeptides into the aqueous (hydrophilic) phase. This apparently paradoxical behavior is also exhibited by certain integral membrane proteins that aggregate to form channels. The results of gel filtration indicate that the auxin-binding proteins do indeed aggregate strongly and that the polypeptides associate to form a dimer or multimeric complex in vivo. These characteristics are consistent with the hypothesis that the 40-kDa and 42-kDa polypeptides are subunits of a multimeric integral membrane protein which has an auxin-binding site, and which may possess transporter or channel function.

NASA Program Space Biology↗

Size matters: altering the metal-surface coordination in micropores via structural confinement effects

Solid-state NMR experiments were used to investigate the dynamics of supported complexes grafted to a series of silica gel materials of varied pore sizes. Through dipolar recoupling measurements, we found that ligand dynamics were impeded in the more confined environments, as would be expected. A new form of motion involving the complex as a whole, however, appeared in the most restricted environment consisting of 22 Å diameter pores. These motions persisted down to –100 °C at which point the ligands were frozen on the NMR timescale. The newly observed dynamics could only result from the breaking of secondary dative metal–siloxane interactions that otherwise lock the complex in a preferred orientation on the surface. Crucially, these results show that confinement effects alone can be sufficient to reduce a grafted metal's effective coordination number in direct analogy to the synthesis of undercoordinated complexes using bulky ligands. Finally, this finding could have important implications in the synthesis of more active heterogeneous catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

CCAAT/enhancer-binding protein delta is a critical regulator of insulin-like growth factor-I gene transcription in osteoblasts

Insulin-like growth factor-I (IGF-I) plays a major role in promoting skeletal growth by stimulating bone cell replication and differentiation. Prostaglandin E2 and other agents that induce cAMP production enhance IGF-I gene transcription in cultured rat osteoblasts through a DNA element termed HS3D, located in the proximal part of the major rat IGF-I promoter. We previously determined that CCAAT/enhancer-binding protein delta (C/EBPdelta) is the key cAMP-stimulated regulator of IGF-I transcription in these cells and showed that it transactivates the rat IGF-I promoter through the HS3D site. We now have defined the physical-chemical properties and functional consequences of the interactions between C/EBPdelta and HS3D. C/EBPdelta, expressed in COS-7 cells or purified as a recombinant protein from Escherichia coli, bound to HS3D with an affinity at least equivalent to that of the albumin D-site, a known high affinity C/EBP binding sequence, and both DNA elements competed equally for C/EBPdelta. C/EBPdelta bound to HS3D as a dimer, with protein-DNA contact points located on guanine residues on both DNA strands within and just adjacent to the core C/EBP half-site, GCAAT, as determined by methylation interference footprinting. C/EBPdelta also formed protein-protein dimers in the absence of interactions with its DNA binding site, as indicated by results of glutaraldehyde cross-linking studies. As established by competition gel-mobility shift experiments, the conserved HS3D sequence from rat, human, and chicken also bound C/EBPdelta with similar affinity. We also found that prostaglandin E2-induced expression of reporter genes containing human IGF-I promoter 1 or four tandem copies of the human HS3D element fused to a minimal promoter and show that these effects were enhanced by a co-transfected C/EBPdelta expression plasmid. Taken together, our results provide evidence that C/EBPdelta is a critical activator of IGF-I gene transcription in osteoblasts and potentially in other cell types and species.

NASA Discipline Musculoskeletal↗

Phase transformations in xerogels of mullite composition

Monophasic and diphasic xerogels have been prepared as precursors for mullite (3Al2O3-2SiO2). Monophasic xerogel was synthesized from tetraethyl orthosilicate and aluminum nitrate nanohydrate and the diphasic xerogel from colloidal suspension of silica and boehmite. The chemical and structural evolutions, as a function of thermal treatment, in these two types of sol-gel derived mullite precursor powders have been characterized by DTA, TGA, X-ray diffraction, SEM and infrared spectroscopy. Monophasic xerogel transforms to an Al-Si spinel from an amorphous structure at approximately 980 C. The spinel then changes into mullite on further heating. Diphasic xerogel forms mullite at approximately 1360 C. The components of the diphasic powder react independently up to the point of mullite formation. The transformation in the monophasic powder occurs rapidly and yields strongly crystalline mullite with no other phases present. The diphasic powder, however, transforms rather slowly and contains remnants of the starting materials (alpha-Al2O3, cristobalite) even after heating at high temperatures for long times (1600 C, 6 hr). The diphasic powder could be sintered to high density but not the monophasic powder in spite of its molecular level homogeneity.

Hyatt, Mark J.↗

Phase transformations in xerogels of mullite composition

Monophasic and diphasic xerogels have been prepared as precursors for mullite (3Al203-2Si02). Monophasic xerogel was synthesized from tetraethyl orthosilicate and aluminum nitrate nanohydrate and the diphasic xerogel from colloidal suspension of silica and boehmite. The chemical and structural evolutions, as a function of thermal treatment, in these two types of sol-gel derived mullite precursor powders have been characterized by DTA, TGA, X-ray diffraction, SEM and infrared spectroscopy. Monophasic xerogel transforms to an Al-Si spinel from an amorphous structure at approximately 980 C. The spinel then changes into mullite on further heating. Diphasic xerogel forms mullite at approximately 1360 C. The components of the diphasic powder react independently up to the point of mullite formation. The transformation in the monophasic powder occurs rapidly and yields strongly crystalline mullite with no other phases present. The diphasic powder, however, transforms rather slowly and contains remnants of the starting materials (alpha-Al203, cristobalite) even after heating at high temperatures for long times (1600 C, 6 hr). The diphasic powder could be sintered to high density but not the monophasic powder in spite of its molecular level homogeneity.

Hyatt, Mark J.↗

Control over emergence and alignment of transient blisters in thermo-responsive gels using hierarchically patterned substrates

Surfaces with tunable microscale textures are vital in a large variety of technological applications, including heat transfer, antifouling and adhesion. To facilitate such broad-scale use, there is a need to create surfaces that undergo reconfigurable changes in topology and thus, enable switchable functionality. To date, there is a relative dearth of methods for engineering surfaces that can be actuated to change topography over a range of length scales, and hence, form tunable hierarchically structured layers. Combining modeling and experiments, we design a geometrically patterned, thermo-responsive poly (N-isopropylacrylamide) gel film that undergoes controllable hierarchical changes in topology with changes in temperature. At the bottom, the film is covalently bound to a solid, curved substrate; at the top, the film encompasses longitudinal rectangular ridges that are oriented perpendicular to the underlying cylindrical curves. At temperatures below lower critical solution temperature (LCST), the swollen gel exhibits 3D variations in polymer density and thickness defined by the gel's top and bottom topography. As the temperature rises above LCST, the interplay between the upper ridges and lower curves in the gel drives non-uniform, directional solvent transport, the nucleation and propagation of a phase-separated higher-density skin layer, and the resulting pressure buildup within the film. These different, interacting kinetic processes lead to an instability, which produces transient microscopic blisters in the film. Through simulations, we show how tuning the width of the ridges modifies the propagation of a skin layer and creates localized pressure build-up points, which enables control over the emergence, distribution, and alignment of the microscopic blisters. Futhermore, we provide a simple argument to predict the size of such microscopic features. Experiments confirm our predictions and further highlight how our computational model enables the rational design of topographical transitions in these tunable films. The development of actuatable, hierarchically structured films provides new routes for achieving switchable functionality in actuators, drug release systems and adhesives.

42 ENGINEERING↗

Direct Conversion of CO 2 to Olefins over a Cr 2 O 3 /ZSM-5@CaO Cooperative and Bifunctional Material Under Isothermal Conditions

Direct conversion of point-source CO 2 into fine chemicals over cooperative and bifunctional materials (BFMs) – composed of adsorbents and catalysts – has emerged as a promising approach to improve the energy efficiency of the carbon capture and conversion processes. In this study, a bifunctional material consisting of Cr 2 O 3 /ZSM-5 catalyst and CaO adsorbent was developed and tested in the CO 2 -oxidative dehydrogenation of propane (CO 2 –ODHP) for reactive capture of CO 2 in a fixed bed reactor. First, CaO was prepared using two distinct methods: solid-state and citrate sol–gel. The citrate sol–gel method resulted in small and finely-distributed CaO particles, allowing more accessible sites for CO 2 adsorption. Consequently, a high CO 2 adsorption capacity of ~14 mmol/g was achieved with fast adsorption kinetics compared to CaO prepared by the solid-state method. The CaO adsorbent was then combined with the Cr 2 O 3 /ZSM-5 catalyst for BFM synthesis and tested in the CO 2 –ODHP process, targeting propylene production. The BFM was extensively characterized to provide insights into the BFM’s surface chemistry, morphology, and reaction mechanism in the reactive capture process of CO 2 –ODHP. The results revealed that under isothermal adsorption–reaction conditions at 600 °C, a propane conversion of 22.5%, a propylene selectivity of 55.3%, and an olefin selectivity of 67.3% were achieved. The excellent propylene selectivity was attributed to the catalyst acidity and redox property of the Cr 2 O 3 /ZSM-5 catalyst, which facilitated the reaction pathway of propane dehydrogenation in the process of CO 2 –ODHP. Overall, this study renders Cr 2 O 3 /ZSM-5@CaO as promising BFMs with high CO 2 capture capacity and catalytic activity for integrated CO 2 capture and conversion in the ODHP reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of Doping on Thermal Conductivity of Pyrochlore Oxides for Advanced Thermal Barrier Coatings

Pyrochlore oxides of general composition, A2B2O7, where A is a 3(+) cation (La to Lu) and B is a 4(+) cation (Zr, Hf, Ti, etc.) have high melting point, relatively high coefficient of thermal expansion, and low thermal conductivity which make them suitable for applications as high-temperature thermal barrier coatings. The effect of doping at the A site on the thermal conductivity of a pyrochlore oxide La2Zr2O7, has been investigated. Oxide powders of various compositions La2Zr2O7, La(1.7)Gd(0.3)Zr2O7, La(1.7)Yb(0.3)Zr2O7 and La(1.7)Gd(0.15)Yb(0.15)Zr2O7 were synthesized by the citric acid sol-gel method. These powders were hot pressed into discs and used for thermal conductivity measurements using a steady-state laser heat flux test technique. The rare earth oxide doped pyrochlores La(1.7)Gd(0.3)Zr2O7, La(1.7)Yb(0.3)Zr2O7 and La(1.7)Gd(0.15)Yb(0.15)Zr2O7 had lower thermal conductivity than the un-doped La2Zr2O7. The Gd2O3 and Yb2O3 co-doped composition showed the lowest thermal conductivity.

Bansal, Narottam P.↗

Enabling Industrial Re-Use of Large-Format Additive Manufacturing Molding and Tooling

Large-format additive manufacturing (LFAM) is an enabling manufacturing technology capable of producing large parts with highly complex geometries for a wide variety of applications, including automotive, infrastructure/construction, and aerospace mold and tooling. In the past decade, the LFAM industry has seen widespread use of bio-based, glass, and/or carbon fiber reinforced thermoplastic composites which, when printed, serve as a lower-cost alternative to metallic parts. One of the highest-volume materials utilized by the industry is carbon fiber (CF)-filled polycarbonate (PC), which in out-of-autoclave applications can achieve comparable mechanical performance to metal at a significantly lower cost. Previous work has shown that if this material is recovered at various points throughout the manufacturing process for both the lab and pilot scale, it can be mechanically recycled with minimal impacts on the functional performance and printability of the material while significantly reducing the feedstock costs. End-of-life (EOL) CF-PC components were processed through industrial shredding, melt compounding, and LFAM equipment, followed by evaluation of the second-life material properties. Experimental assessments included quantitative analysis of fiber length attrition, polymer molecular weight degradation using gel permeation chromatography (GPC), density changes via pycnometry, thermal performance using dynamic mechanical analysis (DMA), and mechanical performance (tensile properties) in both the X- and Z-directions. Results demonstrated a 24.6% reduction in average fiber length compared to virgin prints, accompanied by a 21% decrease in X-direction tensile strength and a 39% reduction in tensile modulus. Despite these reductions, Z-direction tensile modulus improved by 4%, density increased by 6.8%, and heat deflection temperature (HDT) under high stress retained over 97% of its original value. These findings underscore the potential for integrating mechanically recycled CF-PC into industrial LFAM applications while highlighting the need for technological innovations to mitigate fiber degradation and enhance material performance for broader adoption. This critical step toward circular material practices in LFAM offers a pathway to reducing feedstock costs and environmental impact while maintaining functional performance in industrial applications.

additive manufacturing↗

LCO Synthesis by Sol-Gel Method

The synthesis of Lanthanum Cobalt Oxide (LCO) via Sol-Gel method provides a potentially low-cost method of production for a P-type photocatalytic. LCO was prepped from Lanthanum and Nitrate Precursors in Aqueous solution. After a significant amount of water is evaporated, the solution is deposited onto SiO2 substrate via spin-deposition method. After annealing, the samples produce thin film LCO that display thickness of sub-500 nanometers. The samples material profile is confirmed by both Raman spectroscopy and X-Ray Diffraction spectroscopy (XRD). Additionally, two-point probing tested the conductivity of the samples. The thin film samples display characteristics of a P-type photocatalytic and may potentially be used in the formation of a P-N junction for user in water-splitting applications.

36 MATERIALS SCIENCE↗