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29 records · Page 2

Selective Plasma Deposition of Fluorocarbon Films on SAMs

A dry plasma process has been demonstrated to be useful for the selective modification of self-assembled monolayers (SAMs) of alkanethiolates. These SAMs are used, during the fabrication of semiconductor electronic devices, as etch masks on gold layers that are destined to be patterned and incorporated into the devices. The selective modification involves the formation of fluorocarbon films that render the SAMs more effective in protecting the masked areas of the gold against etching by a potassium iodide (KI) solution. This modification can be utilized, not only in the fabrication of single electronic devices but also in the fabrication of integrated circuits, microelectromechanical systems, and circuit boards. In the steps that precede the dry plasma process, a silicon mold in the desired pattern is fabricated by standard photolithographic techniques. A stamp is then made by casting polydimethylsiloxane (commonly known as silicone rubber) in the mold. The stamp is coated with an alkanethiol solution, then the stamp is pressed on the gold layer of a device to be fabricated in order to deposit the alkanethiol to form an alkanethiolate SAM in the desired pattern (see figure). Next, the workpiece is exposed to a radio-frequency plasma generated from a mixture of CF4 and H2 gases. After this plasma treatment, the SAM is found to be modified, while the exposed areas of gold remain unchanged. This dry plasma process offers the potential for forming masks superior to those formed in a prior wet etching process. Among the advantages over the wet etching process are greater selectivity, fewer pin holes in the masks, and less nonuniformity of the masks. The fluorocarbon films formed in this way may also be useful as intermediate layers for subsequent fabrication steps and as dielectric layers to be incorporated into finished products.

Crain, Mark M., III↗

Powder Extinguishants for Jet-Fuel Fires

Mixtures of alkali metal dawsonite and metal halide show superior performance. In tests of new dry powder fire extinguishants, mixtures of potassium dawsonite with either stannous iodide or potassium iodide found effective for extinguishing jet-fuel fires on hot metal surfaces (up to 900 degrees C). Mixtures performed more effectively than either compound alone.

Altman, R. L.↗

Antineoplastic activity of Salmonella Typhimurium outer membrane nanovesicles

Highlights: • ST-OMVs is a promising antitumor monotherapy or as an adjuvant to chemotherapies. • ST-OMVs downregulated Ki-67 and upregulated CD49b immune-expression. • ST-OMVs downregulated angiogenesis by inhibiting VEGF gene expression. • ST-OMVs increased tumor cells apoptosis and autophagy (increased caspase-3and Beclin1). Nano-sized Gram-negative bacterial outer membrane vesicles possess unique structural and immunostimulatory effects that could be exploited to regress tumors by alerting the host immune system and reversing the immunosuppressive tumor microenvironment. The current study was conducted to investigate the antitumor activity of the outer membrane vesicles (ST-OMVs) of Salmonella Typhimurium ATCC 14028, in vitro in human colorectal carcinoma (HTC116), breast cancer (MCF-7), and hepatocellular carcinoma (HepG2) cell lines and in vivo in Ehrlich solid carcinoma-bearing mice model either as a mono-immunotherapy or as an adjuvant to a commonly used conventional chemotherapy. In addition, we investigated the safety of ST-OMVs. Adult Swiss albino female mice with transplanted Ehrlich solid carcinoma were treated with either ST-OMVs, paclitaxel or a combination of both. Tumor volume, growth inhibition rate, quantitative RT-PCR of Bax and VEGF genes expression, histopathology and immune-expression of caspase-3, Beclin-1, CD49b and Ki-67 were all analyzed. Our results showed that ST-OMVs significantly decreased tumor volume, significantly increased tumor growth inhibition rate, up-regulated the immunohistochemical expression of caspase-3, Beclin-1, and CD49b (enhanced recruitment of NK cells). Furthermore, ST-OMVs down-regulated the expression of Ki-67, increased Bax gene expression and decreased VEGF gene expression as detected by qRT-PCR analysis. Histologically, ST-OMVs promoted apoptosis, decreased tumor invasion and mitotic activities. Moreover, ST-OMVs showed a remarkable cytotoxic activity in various investigated in vitro cancer cell lines. Our findings demonstrate potential antitumor activity of ST-OMVs that might be used as a promising safe antitumor immunotherapy or an adjuvant to conventional chemotherapeutic drugs, resolving some of their problems.

60 APPLIED LIFE SCIENCES↗

Biogeochemistry of the Antrim Shale Natural Gas Reservoir

The Antrim Shale, located in the Michigan Basin, United States (U.S.), is a major U.S. shale play having produced over 2.5 Trillion Cubic Feet (Tcf) of unconventional shale natural gas as of 2010. The shallow nature of this formation sets it apart from other, more characterized unconventional shale gas plays. The depth of gas production of the Antrim ranges from approximately 150 to 600 m and it is typically vertically drilled, contrary to deeper, horizontally drilled shales. A thorough understanding of the biogeochemistry and microbiology of this complex system will be advantageous for improving well performance, produced water management, and potential biocidal treatment as microbial community composition can vary substantially even among closely spaced wells. In this study, we analyzed produced water collected from nine different wells in the Antrim Shale by investigating the geochemical and microbial community composition of the produced water to gain greater insight into the overall biogeochemistry of this unique shale system. The majority of the wells from this study had high total dissolved solids (TDS) primarily composed of chloride and sodium, averaging 86,804 mg/L with a maximum 116,223 mg/L; however, three of the wells sampled along the northern margin of the basin exhibited significantly lower TDS ranging from 4932 to 6496 mg/L. Overall, our microbial community analysis revealed relatively low abundance within our samples and high variability of the microbial community among the sampled wells. The majority of bacterial sequences were identified within Proteobacteria, Firmicutes, and Actinobacteria phyla and metagenomic sequencing revealed the low presence of Methanobacteriaceae within each sample. We also investigated potential microbial community drivers and found that TDS, sodium, chloride, iodide, bromide, ammonium, potassium, and strontium were significantly correlated with the observed microbial community. The varying geochemical conditions between wells demonstrate different subsurface environmental niches, potentially driving the heterogeneous microbial communities we observed from well to well. This analysis suggests an important relationship between both well location and geochemistry and the observed microbial community that can persist in the reservoir. Continued studies of the Antrim Shale will improve our understanding of the complex interdependencies of this ecosystem.

03 NATURAL GAS↗

Preparation and Characterization of Fluorescent Derivatives of Chicken Egg White Lysozyme

Fluorescence is one of the most versatile and powerful tools for the study of macromolecules. While most proteins are intrinsically fluorescent, working at crystallization concentrations require the use of covalently prepared derivatives added as tracers. This approach requires derivatives that do not markedly affect the crystal packing. We have prepared a number of fluorescent derivatives of chicken egg white lysozyme with probes bound to one of two different sites on the protein molecule. Lucifer yellow, cascade blue, and 5-(2-aminoethyl)aminonapthalene-l-sulfonic acid (EDANS) have been attached to the side chain carboxyl of asp101 using a carbodiimide coupling procedure. asp101 lies within the active site cleft, and it is believed that the probes are at least partially "buried" within that cleft. Lucifer yellow and MANS probes with iodoacetamide reactive groups have been bound to hisl5, located on the "back side" of the molecule relative to the active site. The fluorescently labeled protein is readily purified from the starting material by cation exchange chromatography. All the derivatives fluoresce in both the solution and the crystalline states. Fluorescence characterization has focused on determining the bound probe quantum yields, lifetimes, absorption and emission spectra, and quenching by added solutes in comparison to the free probe. No appreciable changes are found in the lifetimes of any of the probes except for cascade blue, where Tau(sub free) = 3.52 ns vrs Tau(sub bound) = 2.8 ns. Spectral shifts are found in most cases. Particularly strong quenching upon binding is found in the case of the cascade blue derivative, likely due to probe interactions with the active site cleft. While none of the asp101 bound probes are well quenched by commonly employed solutes, such as potassium and sodium iodide, acrylamide, primuline, the chloride salts of manganese, cesium, and cobalt, trifluoroacetamide, trichloroethanol, and thallium iodide, in those cases where quenching is observed the bound probe is less efficiently quenched relative to the free probe. This indicates that the bound probes are less accessible to the bulk solution, an expected finding for attachment within the active site cleft. Attempts have been made to bind other molecules to these sites, with varying success. Interestingly, all three probes contain one or more sulfonate ((Ar-S03)-) groups. We have not been successful in binding analogous probes without sulfate groups such as pyrene, or with derivatized sulfonate groups such as dansyl type probes, analogous to MANS but where the sulfonate group is derivatized, Ar-S02-N2C2H7. None of the probes is rigidly bound to the protein, i.e., they all have a probe motion superimposed on that of the protein.

Sumida, John↗

Development of a Reference Dose for Perchlorate: Current Issues and Status

The perchlorate anion (ClO4) is typically manufactured as the ammonium salt. The most common use of ammonium perchlorate is in the aerospace program as a component of solid rocket fuel. The perchlorate anion is exceedingly stable under environmental conditions and has been found in ground and surface waters in CA, NV, UT, AZ, TX, AK, NY, MD, WV and FL. The National Center for Environmental Assessment (NCEA) of the U.S. Environmental Protection Agency (US EPA) is in the process of developing an oral reference dose (RfD) for perchlorate. An oral RfD is a body-weight-adjusted dose that can be consumed daily over an entire lifetime with the expectation of no adverse health effects. Once developed, the new RfD will be used by US EPA as the basis of a safe-drinking-water level (SDWL) guideline. US EPA and regional regulatory agencies will then jointly or separately propose clean-up action levels for ground and surface waters at contaminated sites. The toxicological database on CIO4- as of March 1997 was determined by an expert peer-review panel to be inadequate for the purpose of deriving an oral RfD. For example, little or no experimental data existed on the subchronic, reproductive, or developmental toxicity of perchlorate. To fill gaps in the toxicological database, eight animal studies were designed by a government-industry consortium that included US EPA and AFRL. These studies were performed in 1997-1998. It has been known for many years that in the thyroid, high doses of perchlorate block the function of iodide by competing for iodide binding sites. Perchlorate was used in the 1950s-60s as a treatment for Graves' disease (a hyperthyroid condition). Because of what was already known about the pharmacological mode of action of perchlorate, specific concerns addressed in the design of the recent animal studies included the potential for developmental toxicity, notably neurological development. Upon review of complete study reports from four of the studies and incomplete data from the other two, US EPA/NCEA issued a document in December 1998 stating that the critical effects were hormone and histology data from the neurodevelopmental/behavioral toxicity study that had been performed in rats; an RfD was proposed based upon the observation of thyroid-follicular-cell hypertrophy in the 5-day-old pups (PND) of dams given perchlorate in drinking water at 0.1 mg/kg-day (the lowest dose tested) in this study. US EPA/NCEA also focused attention on a nonsignificant increase in motor activity observed in 14-day-old male pups in the same study at the same dose. In February 1999, a public workshop was convened at which an external peer-review panel determined that there was still insufficient data to support the development of a RfD. Additional studies were recommended. Since that time a clinical study revealed significant depression of thyroidal uptake of iodide in volunteers receiving potassium perchlorate at 10 mg/day for 14 days. Follow-up studies currently underway include a pathology working-group review of histology slides from the all of the previous studies, a motor activity study similar to the first behavioral study, an additional immunotoxicity study, male and female rat kinetic studies, a hormone interlaboratory study, and an effects study for thyroid and brain in developing rats. These studies are expected to be complete by mid-2000. A clinical study is planned to determine inhibition of iodide uptake and kinetic parameters in humans following 14-day perchlorate ingestion. The kinetics studies will provide data for developing physiologically based pharmacokinetic (PBPK) models for rats and humans needed to establish the RfD.

Pleus, R. C.↗

Computational and experimental analysis of structural and Thermophysical properties of LiX-KX (X = chloride, iodide, or bromide) molten salts

Molten salts containing lithium (Li) and potassium (K) halides, including chlorides (Cl), bromides (Br), and iodides (I), are pivotal in advanced technological applications including nuclear reactor technologies, thermal batteries, and industrial pyrochemical processes. Despite their significance, the availability of the temperature-dependent structural and thermophysical properties of these molten salts remain scarce. Here, this study addresses this knowledge gap by predicting and measuring the key properties such as coordination number, radial distribution function, density, heat capacity, and volumetric thermal expansion of molten LiI-KI, LiBr-KBr and LiCl-KCl eutectic mixtures. Utilizing ab initio molecular dynamics (AIMD) simulations, we predict these properties of LiX-KX (X=Br,I, Cl) across various temperatures, with chlorides as a benchmark. Experimental measurements using Archimedes methods and Differential Scanning Calorimetry validate the densities and heat capacities of these molten salts. Our comprehensive analysis of the structural and thermophysical properties provides critical insights into the behavior of these molten salts at various temperatures, enhancing the understanding necessary for their application in advanced technologies.

36 - MATERIALS SCIENCE↗

Challenges in selecting appropriate electrodes for high-temperature molten salt systems

Based on a specific molten salt (e.g., chloride, fluoride, iodide) investigated, different working and reference electrode materials can be selected considering the chemical and thermal stability of the electrochemical cell components. In this talk, the electrode materials and challenges encountered with a spectro-electrochemical setup installed inside a glovebox, and the solutions implemented to address these challenges, specifically for the chloride and iodide molten salts will be presented. For molten chlorides, the fundamental interactions between neodymium chloride (NdCl3) and Nd metal in lithium chloride-potassium chloride eutectic salt were investigated at 773 K. The electrochemical transitions Nd2+,3+/Nd(s) were analyzed using an inert W electrode with cyclic voltammetry and chronoamperometry techniques, coupled with in-situ UV-Vis spectroscopy to elucidate the kinetic pathways of this disproportionation reaction (eq. 1). Nd(s) + NdCl3 = NdCl2 (1) For molten iodides, the challenges related to working electrode selectivity and present spectro-electrochemical results obtained from cyclic voltammetry measurements conducted at 673 K will be discussed.

36 - MATERIALS SCIENCE↗

Permeation of halide anions through phospholipid bilayers occurs by the solubility-diffusion mechanism

Two alternative mechanisms are frequently used to describe ionic permeation of lipid bilayers. In the first, ions partition into the hydrophobic phase and then diffuse across (the solubility-diffusion mechanism). The second mechanism assumes that ions traverse the bilayer through transient hydrophilic defects caused by thermal fluctuations (the pore mechanism). The theoretical predictions made by both models were tested for halide anions by measuring the permeability coefficients for chloride, bromide, and iodide as a function of bilayer thickness, ionic radius, and sign of charge. To vary the bilayer thickness systematically, liposomes were prepared from monounsaturated phosphatidylcholines (PC) with chain lengths between 16 and 24 carbon atoms. The fluorescent dye MQAE (N-(ethoxycarbonylmethyl)-6-methoxyquinolinium bromide) served as an indicator for halide concentration inside the liposomes and was used to follow the kinetics of halide flux across the bilayer membranes. The observed permeability coefficients ranged from 10(-9) to 10(-7) cm/s and increased as the bilayer thickness was reduced. Bromide was found to permeate approximately six times faster than chloride through bilayers of identical thickness, and iodide permeated three to four times faster than bromide. The dependence of the halide permeability coefficients on bilayer thickness and on ionic size were consistent with permeation of hydrated ions by a solubility-diffusion mechanism rather than through transient pores. Halide permeation therefore differs from that of a monovalent cation such as potassium, which has been accounted for by a combination of the two mechanisms depending on bilayer thickness.

NASA Discipline Exobiology↗

Rapid, specific determination of iodine and iodide by combined solid-phase extraction/diffuse reflectance spectroscopy

A new, rapid methodology for trace analysis using solid-phase extraction is described. The two-step methodology is based on the concentration of an analyte onto a membrane disk and on the determination by diffuse reflectance spectroscopy of the amount of analyte extracted on the disk surface. This method, which is adaptable to a wide range of analytes, has been used for monitoring ppm levels of iodine and iodide in spacecraft water. Iodine is used as a biocide in spacecraft water. For these determinations, a water sample is passed through a membrane disk by means of a 10-mL syringe that is attached to a disk holder assembly. The disk, which is a polystyrene-divinylbenzene composite, is impregnated with poly(vinylpyrrolidone) (PVP), which exhaustively concentrates iodine as a yellow iodine-PVP complex. The amount of concentrated iodine is then determined in only 2 s by using a hand-held diffuse reflectance spectrometer by comparing the result with a calibration curve based on the Kubelka-Munk function. The same general procedure can be used to determine iodide levels after its facile and exhaustive oxidation to iodine by peroxymonosulfate (i.e., Oxone reagent). For samples containing both analytes, a two-step procedure can be used in which the iodide concentration is calculated from the difference in iodine levels before and after treatment of the sample with peroxymonosulfate. With this methodology, iodine and iodide levels in the 0.1-5.0 ppm range can be determined with a total workup time of approximately 60 s with a RSD of approximately 6%.

Non-NASA Center↗