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At least 505 records · Page 28
All sourcesNASA NTRSDOE OSTI
NASA NTRS2000

Preparation of Ion Exchange Films for Solid-Phase Spectrophotometry and Solid-Phase Fluorometry

Atomic spectroscopy has dominated the field of trace inorganic analysis because of its high sensitivity and selectivity. The advantages gained by the atomic spectroscopies come with the disadvantage of expensive and often complicated instrumentation. Solid-phase spectroscopy, in which the analyte is preconcentrated on a solid medium followed by conventional spectrophotometry or fluorometry, requires less expensive instrumentation and has considerable sensitivity and selectivity. The sensitivity gains come from preconcentration and the use of chromophore (or fluorophore) developers and the selectivity is achieved by use of ion exchange conditions that favor the analyte in combination with speciative chromophores. Little work has been done to optimize the ion exchange medium (IEM) associated with these techniques. In this report we present a method for making ion exchange polymer films, which considerably simplify the solid-phase spectroscopic techniques. The polymer consists of formaldehyde-crosslinked polyvinyl alcohol with polyacrylic acid entrapped therein. The films are a carboxylate weak cation exchanger in the calcium form. They are mechanically sturdy and optically transparent in the ultraviolet and visible portion of the spectrum, which makes them suitable for spectrophotometry and fluorometry.

Hill, Carol M.↗
NASA NTRS2000

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↗
NASA NTRS2000

A Robust Biomarker

Polymers of bacterial origin, either through cell secretion or the degraded product of cell lysis, form isolated mucoidal strands as well as well-developed biofilms on interfaces. Biofilms are structurally and compositionally complex and are readily distinguishable from abiogenic films. These structures range in size from micrometers to decimeters, the latter occurring as the well-known, mineralised biofilms called stromatolites. Compositionally bacterial polymers are greater than 90 % water, with while the majority of the macromolecules forming the framework of the polymers consisting of polysaccharides (with and some nucteic acids and proteins). These macromolecules contain a vaste amount of functional groups, such as carboxyls, hydroxyls, and phosphoryls which are implicated in cation-binding. It is the elevated metal- binding capacity which provides the bacterial polymer with structural support and also helps to preserves it for up to 3.5 b.y. in the terrestrial rock record. The macromolecules, thus, can become rapidly mineralised and trapped in a mineral matrix. Through early and late diagenesis (bacterial degradation, burial, heat, pressure and time) they break down, losing the functional groups and, gradually, their hydrogen atoms. The degraded product is known as "kerogen". With further diagenesis and metamorphism, all the hydrogen atoms are lost and the carbonaceous matter becomes graphite. until the remnant carbonaceous material become graphitised. This last sentence reads a bit as if ALL these macromolecules break down and end up as graphite., but since we find 441 this is not true for all of the macromolecules. We have traced fossilised polymer and biofilms in rocks from throughout Earth's history, to rocks as old as the oldest being 3.5 b.y.-old. Furthermore, Time of Flight Secondary Ion Mass Spectrometry has been able to identify individual macromolecules of bacterial origin, the identities of which are still being investigated, in all the samples containing fossil biofilm, including the 3.5 b.y..-old carbonaceous cherts from South Africa and Australia. As a result of the unique compositional, structural and "mineralisable" properties of bacterial polymer and biofilms, we conclude that bacterial polymers and biofilms constitute a robust and reliable biomarker for life on Earth and could be a potential biomarker for extraterrestrial life.

Westall, F.↗
NASA NTRS2000

Acetylated Lysozyme as Impurity in Lysozyme Crystals: Constant Distribution Coefficient

Hen egg white lysozyme (HEWL) was acetylated to modify molecular charge keeping the molecular size and weight nearly constant. Two derivatives, A and B, more and less acetylated, respectively, were obtained, separated, purified and added to the solution from which crystals of tetragonal HEWL crystals were grown. Amounts of the A or B impurities added were 0.76, 0.38 and 0.1 milligram per millimeter while HEWL concentration were 20, 30 and 40 milligram per milliliter. The crystals grown in 18 experiments for each impurity were dissolved and quantities of A or B additives in these crystals were analyzed by cation exchange high performance liquid chromatography. All the data for each set of 18 samples with the different impurity and regular HEWL concentrations is well described by one distribution coefficient K = 2.15 plus or minus 0.13 for A and K = 3.42 plus or minus 0.25 for B. The observed independence of the distribution coefficient on both the impurity concentration and supersaturation is explained by the dilution model described in this paper. It shows that impurity adsorption and incorporation rate is proportional to the impurity concentration and that the growth rate is proportional to the crystallizing protein in solution. With the kinetic coefficient for crystallization, beta = 5.10(exp -7) centimeters per second, the frequency at which an impurity molecule near the growing interface irreversibly joins a molecular site on the crystal was found to be 3 1 per second, much higher than the average frequency for crystal molecules. For best quality protein crystals it is better to have low microheterogeneous protein impurity concentration and high supers aturation.

Thomas, B. R.↗
NASA NTRS1999

Challenges to the Transition of IPMC Artificial Muscle Actuators to Practical Application

Ion-exchange membrane metallic composites (IPMC), which were first reported in 1992, are one of the electroactive materials (EAP) with potential applications as artificial muscle actuators. The recent introduction of perfluorocarboxylate-gold composite with tetra-n-butylammonium and Lithium cations instead of sodium made the most significant improvement of the material electroactivity. Under less than 3 volts, IPMC with the new constituents is capable of bending beyond a complete loop. Taking into account the fact that IMPC materials do not induce a significant force, the authors are extensively seeking applications for these bending EAP. Some of the applications that were demonstrated include dust-wiper, catheter guide, miniature motor, robotic-gripper, micro-manipulator, etc. Generally, space applications are the most demanding in terms of operating conditions, robustness and durability, and the co-authors of this paper are jointly addressing the associated challenges. Specifically, a dust-wiper is being developed for the Nanorover's infrared camera window of the MUSES-CN mission. This joint NASA and the Japanese space agency mission, is scheduled to be launch from Kagoshima, Japan, in January 2002, to explore the surface of a small near-Earth asteroid. Several issues that are critical to the operation of IPMC are addressed including the operation in vacuum, low temperatures, and the effect of the electromechanical characteristic of the IPMC on its actuation capability. Highly efficient IPMC materials, mechanical modeling, unique elements and protective coating were introduced by the authors and are making a high probability the success of the IPMC actuated dust-wiper.

Bar-Cohen, Yoseph↗
NASA NTRS1999

The Production of Polycyclic Aromatic Hydrocarbon Anions in Inert Gas Matrices Doped with Alkali Metals. Electronic Absorption Spectra of the Pentacene Anion (C22H14(-))

The absorption spectra of pentacene (C22H14) and its radical cation (C22H14(+)) and anion (C22H14(-)) isolated in inert-gas matrices of Ne, Ar, and Kr are reported from the ultraviolet to the near-infrared. The associated vibronic band systems and their spectroscopic assignments are discussed together with the physical and chemical conditions governing ion (and counterion) production in the solid matrix. In particular, the formation of isolated pentacene anions is found to be optimized in matrices doped with alkali metal (Na and K).

Halasinski, Thomas M.↗
NASA NTRS1999

Sensitive Procedures for Determining the Permeation Resistance of Chlorinated Polyethylene Against Liquid Propellants

The permeation resistance of chlorinated polyethylene (CPE) used in totally encapsulating chemical protective suits against the aerospace fuels hydrazine, monomethylhydrazine, and uns-dimethylhydrazine was determined by measuring the breakthrough time (BT) and time-averaged vapor transmission rate (VTR) using procedures consistent with ASTM F 739 and ASTM F 1383. Two exposure scenarios were simulated: a 2 hour (h) fuel vapor exposure, and a liquid fuel "splash" followed by a 2 h vapor exposure. To simulate internal suit pressure during operation, a positive differential pressure of 0.3 in. water (75 Pa) on the collection side of the permeation apparatus was used. Using the available data, a model was developed to estimate propellant concentrations inside an air-line fed, totally encapsulating chemical protective suit. Concentrations were calculated under simulated conditions of fixed vapor transmission rate, variable breathing air flow rate, and variable splash exposure area. Calculations showed that the maximum allowable permeation rates of hydrazine fuels through CPE were of the order of 0.05 to 0.08 ng/sq cm min for encapsulating suits with low breathing air flow rates (of the order of 5 scfm or 140 L min-1). Above these permeation rates, the 10 parts-per-billion (ppb) threshold limit value time-weighted average could be exceeded. To evaluate suit performance at 10 ppb threshold-limiting value/time-weighted average level concentrations, use of a sensitive analytical method such as cation exchange high performance liquid chromatography with amperometric detection was found to be essential. The analytical detection limit determines the lowest measurable VTR, which in turn governed the lowest per meant concentration that could be calculated inside the totally encapsulating chemical protective suit.

Waller, Jess M.↗
NASA NTRS1999

Bond Dissociation Energies of the Tungsten Fluorides and Their Singly-Charged Ions: A Density Functional Survey

The dissociation of WF6 and the related singly-charged cations and anions into the lower fluorides and fluorine atoms has been investigated theoretically using density functional theory (B3LYP) and relativistic effective core potentials, with estimates of spin-orbit effects included using a simple model. The inclusion of spin-orbit is essential for a correct description of the thermochemistry. The total atomization energy of the neutral and anionic WF6 is reproduced to within 25 kcal/mol, but comparison of individual bond dissociation energies with available experimental data shows discrepancies of up to 10 kcal/mol. The results are nevertheless useful to help resolve discrepancies in experimental data and provide estimates of missing data.

Dyall, Kenneth G.↗
NASA NTRS2000

BOREAS TE-1 SSA Soil Lab Data

This data set was collected by TE-1 to provide a set of soil properties for BOREAS investigators in the SSA. The soil samples were collected at sets of soil pits in 1993 and 1994. Each set of soil pits was in the vicinity of one of the five flux towers in the BOREAS SSA. The collected soil samples were sent to a lab, where the major soil properties were determined. These properties include, but are not limited to, soil horizon; dry soil color; pH; bulk density; total, organic, and inorganic carbon; electric conductivity; cation exchange capacity; exchangeable sodium, potassium, calcium, magnesium, and hydrogen; water content at 0.01, 0.033, and 1.5 MPascals; nitrogen; phosphorus; particle size distribution; texture; pH of the mineral soil and of the organic soil; extractable acid; and sulfur. The data are stored in tabular ASCII text files. The data files are available on a CD-ROM (see document number 20010000884), or from the Oak Ridge National Laboratory (ORNL) Distributed Active Archive Center (DAAC).

Hall, Forrest G.↗
NASA NTRS2000

BOREAS TE-2 NSA Soil Lab Data

This data set contains the major soil properties of soil samples collected in 1994 at the tower flux sites in the Northern Study Area (NSA). The soil samples were collected by Hugo Veldhuis and his staff from the University of Manitoba. The mineral soil samples were largely analyzed by Barry Goetz, under the supervision of Dr. Harold Rostad at the University of Saskatchewan. The organic soil samples were largely analyzed by Peter Haluschak, under the supervision of Hugo Veldhuis at the Centre for Land and Biological Resources Research in Winnipeg, Manitoba. During the course of field investigation and mapping, selected surface and subsurface soil samples were collected for laboratory analysis. These samples were used as benchmark references for specific soil attributes in general soil characterization. Detailed soil sampling, description, and laboratory analysis were performed on selected modal soils to provide examples of common soil physical and chemical characteristics in the study area. The soil properties that were determined include soil horizon; dry soil color; pH; bulk density; total, organic, and inorganic carbon; electric conductivity; cation exchange capacity; exchangeable sodium, potassium, calcium, magnesium, and hydrogen; water content at 0.01, 0.033, and 1.5 MPascals; nitrogen; phosphorus: particle size distribution; texture; pH of the mineral soil and of the organic soil; extractable acid; and sulfur. These data are stored in ASCII text files. The data files are available on a CD-ROM (see document number 20010000884), or from the Oak Ridge National Laboratory (ORNL) Distributed Active Archive Center (DAAC).

Veldhuis, Hugo↗
NASA NTRS2001

Detection of Soluble and Fixed NH4+ in Clay Minerals by DTA and IR Reflectance Spectroscopy : A Potential Tool for Planetary Surface Exploration

Nitrogen is an essential element for life. It is the only element among the six major biogenic elements, C, O, S, O, P, H, whose presence in the Martian soil has not been positively and directly established. We describe here a study assessing the ability to detect NH4 in soils by two methods: differential thermal analysis (DTA) and infrared (IR) reflectance spectroscopy. Four standard clay minerals (kaolinite, montmorillonite, illite and attapulgite) and an altered tephra sample from Mauna Kea were treated with NH4 in this study. Samples of the NH4-treated and leached clays were analyzed by DTA and infrared (IR) reflectance spectroscopy to quantify the delectability of soluble and sorbed/fixed NH4. An exotherm at 270-280 C was clearly detected in the DTA curves of NH4-treated (non-leached) samples. This feature is assigned to the thermal decomposition reaction of NH4. Spectral bands observed at 1.56, 2.05, 2.12, 3.06, 3.3, 3.5, 5.7 and 7.0 microns in the reflectance spectra of NH4-treated and leached samples are assigned to the sorbed/fixed ammonium in the clays. The montmorillonite has shown the most intense absorbance due to fixed ammonium among the leached samples in this study, as a result of its high cation sorption capacity. It is concluded that the presence of sorbed or fixed NH4 in clays may be detected by infrared (IR) reflectance or emission spectroscopy. Distinction between soluble and sorbed NH4 may be achieved through the presence or absence of several spectral features assigned to the sorbed NH4 moietyi and, specifically, by use of the 4.2 micrometer feature assigned to solution NH4. Thermal analyses furnish supporting evidence of ammonia in our study through detection of N released at temperatures of 270-330 C. Based on these results it is estimated that IR spectra measured from a rover should be able to detect ammonia if present above 20 mg NH4/g sample in the surface layers. Orbital IR spectra and thermal analyses measured on a rover may be able to detect ammonia in soils as well but at higher abundances. The spectral features at 3.06 and 7.0 microns due to bound NH4 in clays and altered Hawaiian tephra appear to be the most promising for detection by orbital spectrometers. If N species are present on Mars the sedimentary deposits may be the best regions to look for them.

Janice, Bishop↗
NASA NTRS2001

Thermodynamic Database for the NdO(1.5)-YO(1.5)-YbO(1.5)-ScO(1.5)-ZrO2 System

A database for YO(1.5)-NdO(1.5)-YbO(1.5)-ScO(1.5)-ZrO2 for ThermoCalc (ThermoCalc AB, Stockholm, Sweden) has been developed. The basis of this work is the YO(1.5)-ZrO2 assessment by Y. Du, Z. Jin, and P. Huang, 'Thermodynamic Assessment of the ZrO2-YO(1.5) System'. Experimentally only the YO(1.5)-ZrO2 system has been well-studied. All other systems are only approximately known. The major simplification in this work is the treatment of each single cation unit as a component. The pure liquid oxides are taken as reference states and two term lattice stability descriptions are used for each of the components. The limited experimental phase diagrams are reproduced.

Jacobson, Nathan S.↗
NASA NTRS1995

The Ozonide Anion: A Theoretical Study

Complete active space self-consistent field (CASSCF) and CASSCF second order perturbation theory (CASPT2) methods have been used for the geometry optimization and calculation of harmonic and fundamental frequencies of the ozonide ion O3(-) and the ozonide lithium complex Li(+)O3(-). For O3(-) harmonic frequencies have also been obtained using the coupled-cluster method, CCSD(T). Infrared intensities are computed from dipole moment derivatives at the CASSCF level. The predicted equilibrium geometry for O3(-) is: Roo = 1.361 Angstroms and angle ooo = 115.4 degrees, and the fundamental frequencies are: nu(sub 1) = 989 per centimeter, nu(sub 2) 556 per centimeter, nu(sub 3) = 870 per centimeter (experimental values are: Roo =1.36 plus or minus 0.02 Angstroms, angle (ooo) = 111.8 plus or minus 2.0 degrees, nu(sub 1) = 975(50) per centimeter, nu(sub 2) = 550(50) per centimeter, nu(sub 3) = 880(50) per centimeter). Corresponding data for the lithium ozonide complex have also been obtained. The presented data contradict the previous interpretation of the IR and Raman spectrum obtained after deposition of ozone in N2, argon, or neon matrices with atomic beams of alkali metals. The presence of the lithium cation raises the asymmetric stretch frequency to about 940 per centimeter, which is contradictory to assumptions made in the assignments of the matrix spectra. Calculations made in a dielectric medium strongly suggest that the effect of the matrix on the IR spectrum is small for O3(-) itself. The dissociation and atomization energies of O3(-) are found to be in agreement with experiment.

Borowski, Poitr↗
NASA NTRS1997

Infrared Spectra of Substituted Polycyclic Aromatic Hydrocarbons

Calculations are carried out using density functional theory (DFT) to determine the harmonic frequencies and intensities of 1-methylanthracene, 9-methylanthracene, 9-cyanoanthracene, 2-aminoanthracene, acridine, and their positive ions. The theoretical data are compared with matrix-isolation spectra for these species also reported in this work. The theoretical and experimental frequencies and relative intensities for the neutral species are in generally good agreement, whereas the positive ion spectra are only in qualitative agreement. Relative to anthracene, we find that substitution of amethyl or CN for a hydrogen does not significantly affect the spectrum other than to add the characteristic methyl C-H stretch and C-N stretch (near 2200/cm), respectively. However, addition of NH2 dramatically affects the spectrum of the neutral. Not only are the NH2 modes themselves strong, but this electron withdrawing group induces sufficient partial charge on the ring to give the neutral molecule characteristics of the anthracene cation spectrum. The sum of the absolute intensities is about four times larger for 2-aminoanthracene than for 9-cyanoanthracene. Substituting nitrogen in the ring at the nine position (acridine) does not greatly alter the spectrum compared with anthracene.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1997

The Calculation of Accurate Metal-Ligand Bond Energies

The optimization of the geometry and calculation of zero-point energies are carried out at the B3LYP level of theory. The bond energies are determined at this level, as well as at the CCSD(T) level using very large basis sets. The successive OH bond energies to the first row transition metal cations are reported. For most systems there has been an experimental determination of the first OH. In general, the CCSD(T) values are in good agreement with experiment. The bonding changes from mostly covalent for the early metals to mostly electrostatic for the late transition metal systems.

Bauschlicher, Charles W.↗
NASA NTRS1998

An Infrared Spectroscopic and Density Functional Theoretical Investigation of the Reaction Products of Laser-Ablated Scandium and Titanium Atoms with Nitric Oxide

Laser-ablated Sc and Ti atoms have been reacted with NO during condensation in excess argon. Matrix infrared spectra show that the major products are the side bonded Sc[NO] species and the inserted NScO and NTiO molecules based on isotopic substitution (15NI6O and 15N18O) and DIFT calculations of isotopic frequencies, which provide a match for two modes in three isotopic modifications for each molecule. The NScO and NTiO molecules are nitride/oxides with M-O stretching modes only 46-88/cm below the diatomic metal oxides but M-N stretching modes 314-442/cm lower than the diatomic metal nitride molecules. The ScN, ScO, TiN, and TiO molecules are observed as decomposition products. Evidence is also presented for the nitrosyls ScNO and TiNO, the Sc[NO]+ cation, and the NTiO- anion.

Bauschlicher, Charles W., Jr.↗