Showing papers by "Pacific Northwest National Laboratory published in 1997"

Functionalized Monolayers on Ordered Mesoporous Supports

Abstract: Mesoporous silica materials containing functionalized organic monolayers have been synthesized. Solid-state nuclear magnetic resonance suggests that a cross-linked monolayer of mercaptopropylsilane was covalently bound to mesoporous silica and closely packed on the surface. The relative surface coverage of the monolayers can be systematically varied up to 76 percent. These materials are extremely efficient in removing mercury and other heavy metals from both aqueous and nonaqueous waste streams, with distribution coefficients up to 340,000. The stability of these materials and the potential to regenerate and reuse them have also been demonstrated. The surface modification scheme reported here enables rational design of the surface properties of tailored porous materials and may lead to the synthesis of more sophisticated functionalized composites for environmental and industrial applications.

Theory of Nanometric Optical Tweezers

Abstract: We propose a scheme for optical trapping and alignment of dielectric particles in aqueous environments at the nanometer scale. The scheme is based on the highly enhanced electric field close to a laser-illuminated metal tip and the strong mechanical forces and torque associated with these fields. We obtain a rigorous solution of Maxwell’s equations for the electromagnetic fields near the tip and calculate the trapping potentials for a dielectric particle beyond the Rayleigh approximation. The results indicate the feasibility of the scheme. [S0031-9007(97)03687-9] Optical trapping by highly focused laser beams has been extensively used for the manipulation of submicronsize particles and biological structures [1]. Conventional optical tweezers rely on the field gradients near the focus of a laser beam which give rise to a trapping force towards the focus. The trapping volume of these tweezers is diffraction limited. Near-field optical microscopy enables the optical measurements at dimensions beyond the diffraction limit and makes it possible to optically monitor dynamics of single biomolecules [2]. The potential application of optical near fields to manipulate atoms or nanoparticles has been discussed in Ref. [3]. In this Letter, we present a new methodology for calculating rigorously and self-consistently the trapping forces acting on a nanometric particle in the optical near field and propose a novel high-resolution trapping scheme. The proposed nanometric optical tweezers rely on the strongly enhanced electric field at a sharply pointed metal tip under laser illumination. The near field close to the tip mainly consists of evanescent components which decay rapidly with distance from the tip. The utilization of the metal tip for optical trapping offers the following advantages: (1) The highly confined evanescent fields significantly reduce the trapping volume; (2) the large field gradients result in a larger trapping force; and (3) the field enhancement allows the reduction of illumination power and radiation damages to the sample. High resolution surface modification based on the field enhancement at laser-illuminated metal tips has been recently demonstrated [4]. It is essential to perform a rigorous electromagnetic analysis to understand the underlying mechanism for the field enhancement. Our analysis is therefore relevant not only to optical tweezers, but also to other applications, such as surface modification, nonlinear spectroscopy and near-field optical imaging. To solve Maxwell’s equations in the specific geometry of the tip and its environment, we employ the multiple multipole method (MMP) which recently has been applied to various near-field optical problems [5]. In MMP, electromagnetic fields are represented by a series expansion of known analytical solutions of Maxwell’s equations. To determine the unknown coefficients in the series expansion, boundary conditions are imposed at discrete points on the interfaces between adjacent homogeneous domains. Once the resulting system of equations is solved and the coefficients are determined, the solution is represented by a self-consistent analytical expression. Figure 1 shows our three dimensional MMP simulation of the foremost part of a gold tip (5 nm tip radius) in water for two different monochromatic plane-wave excitations. The wavelength of the illuminating light is l › 810 nm (Ti:sapphire laser), which does not match the surface plasmon resonance. The dielectric constants of tip and water were taken to be « › 224.9 1 1.57i and « › 1.77, respectively [6]. In Fig. 1(a), a plane wave is incident from the bottom with the polarization perpendicular to the tip axis, whereas in Fig. 1( b) the tip is illuminated from the side with the polarization parallel to the tip axis. A striking difference is seen for the two different polarizations: in Fig. 1( b), the intensity

Transfection of a reporter plasmid into cultured cells by sonoporation in vitro

Abstract: Cultured Chinese hamster ovary cells were exposed to 2.25-MHz ultrasound in sterile 4.5-mL polyethylene chambers and tested for cell lysis, sonoporation and DNA transfection. Ten percent of Albunex, a gas-body-based ultrasound contrast agent, was added to ensure cavitation nucleation, and the chambers were rotated at 60 rpm to promote cavitation activity during the 1-min exposures. Uptake of large fluorescent dextran molecules by some cells was observed for spatial peak pressure amplitudes as low as 0.1 MPa, which indicates transient permeabilization and resealing, i.e., sonoporation, of these cells during exposure. Significant lysis occurred for 0.2 MPa, and increased rapidly for exposures above the apparent cavitation threshold (using the H2O2 production test) of about 0.4 MPa spatial peak pressure amplitude. In the DNA transfection tests, 20 micrograms/mL luciferase reporter plasmid was added to the suspension during exposure, and cells were assayed for proliferation ability and luciferase gene expression 2 days after exposure. Cell proliferation was greatly reduced above the cavitation threshold. Luciferase production was significant for 0.20-MPa exposure, and reached 0.33 ng per 10(6) cells at 0.8-MPa exposure. The luciferase production was great for cells exposed in medium supplemented with serum than for cells exposed in serum-free medium. Cells harvested for exposure either in the log phase or in the stationary phase of culture gave similar proliferation and transfection results. The effects essentially disappeared when the Albunex was omitted from the suspension and the tube was not rotated. Thus, sonoporation by ultrasonic cavitation in the rotating tube system yields plasmid transfection with subsequent transient gene expression.

Effects of pH on Heavy Metal Sorption on Mineral Apatite

Abstract: The sorption of aqueous Pb, Cd, and Zn onto a mineral apatite from North Carolina was investigated in relation to a wide range of pH. The effects of pH on solid-phase precipitation were particularly emphasized. The heavy metals were applied as single or multiple species. Solution pH greatly affected metal sorption mechanism by apatite and metal−apatite reaction products. The sorption of aqueous Pb was primarily through a process of the dissolution of apatite followed by the precipitation of variable pyromorphite-type minerals under acidic condition or of hydrocerussite [Pb3(CO3)2(OH)2] and lead oxide fluoride (Pb2OF2) under alkaline condition. Otavite (CdCO3), cadmium hydroxide [Cd(OH)2], and zincite (ZnO) were formed in the Cd or Zn system, especially under alkaline condition; while hopeite [Zn3(PO4)2·4H2O] might precipitate only under very acidic condition. Alternative sorption mechanisms other than precipitation of the crystalline phases were important in reducing Cd and Zn concentrations by the apatit...

Radiation effects in glasses used for immobilization of high-level waste and plutonium disposition

Abstract: This paper is a comprehensive review of the state-of-knowledge in the field of radiation effects in glasses that are to be used for the immobilization of high-level nuclear waste and plutonium disposition. The current status and issues in the area of radiation damage processes, defect generation, microstructure development, theoretical methods and experimental methods are reviewed. Questions of fundamental and technological interest that offer opportunities for research are identified.

Mesoporous Silica Synthesized by Solvent Evaporation: Spun Fibers and Spray-Dried Hollow Spheres

Abstract: Simple synthesis methods for mesoporous fibers and powders by rapid evaporation of hydrolyzed silicon alkoxide−surfactant solutions are described. Mesoporous fibers are prepared by dry spinning, and mesoporous powders by spray drying of alkoxide−surfactant solutions. Precursor solutions, containing fully hydrolyzed tetraethoxysilane, cetyltrimethylammonium chloride surfactant, and, in the case of the fibers, a fiber-forming polymer, in an acidic alcohol/water mixture, are drawn into continuous filaments or atomized into droplets in a heated air stream. During solvent drying, silica and surfactant self-assemble to form the hexagonally ordered mesophase structure, and all of the nonvolatile components (silica, polymer, and surfactant) are incorporated into the mesophase. The pore diameter and surface area of calcined fibers were 20 A and 1100 m2/g, respectively. For the powders, pore sizes of 25 A and surface areas as high as 1770 m2/g were measured. Spray-dried powders consisting of hollow spherical partic...

Endothelial cell growth and protein adsorption on terminally functionalized, self-assembled monolayers of alkanethiolates on gold

Abstract: The effect of specific chemical functionalities on the growth of bovine aortic endothelial cells (BAEC) was investigated using a set of well-characterized, chemically functionalized surfaces prepared by self-assembly of alkanethiolate monolayers on gold surfaces using the molecules X(CH2)15SH with X = −CH3, −CH2OH, −CO2CH3, and −CO2H. Cells seeded on a substrate in serum-containing culture medium interact with the adsorbed protein layer rather than the substrate. Therefore, the role of two serum proteins, albumin (Alb) (a nonadhesive or blocking protein) and fibronectin (Fn) (an adhesive protein), in cell growth was evaluated by measuring the amount of each protein bound and the tightness of binding (determined by resistance to SDS solubilization) on the self-assembled monolayers (SAMs). BAEC growth varied significantly with surface functionality. Cell growth increased in the following order: −CH2OH < −CO2CH3 < −CH3 ≪ −CO2H, illustrating the effect of specific surface groups. Cell growth on all monolayer...

Low-Level Jet Climatology from Enhanced Rawinsonde Observations at a Site in the Southern Great Plains

Abstract: A climatology of the Great Plains low-level jet (LLJ) is developed from 2 yr of research rawinsonde data obtained up to eight times per day at a site in north-central Oklahoma. These data have better height and time resolution than earlier studies, and show that jets are stronger than previously reported and that the heights of maximum wind speed are closer to the ground. LLJs are present in 47% of the warm season soundings and 45% of the cold season soundings. More than 50% of the LLJs have wind maxima below 500 m above ground level (AGL). Because the 404-MHz radar profiler network in the central United States has its first data points at 500 m AGL, it is likely to miss some LLJ events and will have inadequate vertical resolution of LLJ wind structure. Previous studies have identified LLJs on the basis of a wind speed profile criterion. This criterion fails to separate the classical southerly LLJs from the less frequent northerly jets, which differ in both structure and evolution. Classical sout...

Effect of PCR template concentration on the composition and distribution of total community 16S rDNA clone libraries

Abstract: Total DNA from sediment samples was isolated by a direct lysis technique. Purified DNA was used as template either undiluted or diluted 1:10 prior to polymerase chain reaction (PCR) amplification of 16S rRNA genes. Full-length inserts were analysed for restriction fragment length polymorphisms (RFLP) with the enzyme Cfo1, and the resulting distribution and abundance of RFLP patterns compared between the undiluted and diluted PCR reactions. Results indicate that for low PCR template concentrations, in the range from a few picograms to tens of picograms DNA, proportional representation of specific RFLP types was not reproducible upon template dilution, confirming that PCR amplification of 16S rDNA cannot be used directly to infer microbial abundance. In particular, only 15-24% of the RFLP types recovered from a sample were present in both the undiluted and diluted extracts. We propose that very low template concentrations in the PCR generate random fluctuations in priming efficiency, which led to the contrast in RFLP types observed in the libraries from the undiluted and diluted extracts.

Confined subsurface microbial communities in Cretaceous rock

Abstract: Deep subsurface microbial communities1 are believed to be supported by organic matter that was either deposited with the formation sediments or which migrated from the surface along groundwater flowpaths. Investigation has therefore focused on the existence of microorganisms in recently deposited or highly permeable sediments2,3. Fewer reports have focused on consolidated rocks4–7. These findings have often been limited by inadequate tracer methodology or non-sterile sampling techniques. Here we present evidence for the presence of spatially discrete microbial communities in Cretaceous rocks and advance a mechanism for the long-term survival of these subterranean communities. Samples were collected using aseptic methods and sensitive tracers8. Our results indicate that the main energy source for these communities is organic material trapped within shales. Microbial activity in shales appears to be greatly reduced, presumably because of their restrictive pore size9. However, organic material or its fermentation products could diffuse into adjacent, more permeable sandstones, where microbial activity was much more abundant. This process resulted in the presence of microbial communities at sandstone–shale interfaces. These microorganisms presumably ferment organic matter and carry out sulphate reduction and acetogenesis.

Pore‐size constraints on the activity and survival of subsurface bacteria in a late cretaceous shale‐sandstone sequence, northwestern New Mexico

Abstract: To investigate the distribution of microbial biomass and activities to gain insights into the physical controls on microbial activity and potential long‐term survival in the subsurface, 24 shale and sandstone cores were collected from a site in northwestern New Mexico. Bacterial biomass in the core samples ranged from below detection to 31.9 pmol total phospholipid fatty acid (PLFA) g‐1 of rock with no apparent relationship between lithology and PLFA abundance. No metabolic activities, as determined by anaerobic mineralization of [14C]acetate and [14C]glucose and 35SO4 2‐ reduction, were detected in core samples with pore throats <0.2 fan in diameter, smaller than the size of known bacteria. However, enrichments revealed the presence of sulfate‐re‐ducing bacteria, and 35SO4 2‐ reduction was detected upon extended (14 days) incubation in some small‐pore‐throat samples. In contrast, relatively rapid rates of metabolic activity were more common in core samples containing a significant fraction of pore throat...

Evaluation of heavy metal remediation using mineral apatite

Abstract: The current study investigated the sorption and desorption of dissolved lead (Pb), cadmium (Cd) and zinc (Zn) from aqueous solutions and a contaminated soil by North Carolina mineral apatite. Aqueous solutions of Pb, Cd, and Zn were reacted with the apatite, followed by desorption experiments under a wide variety of pH conditions ranging from 3 to 12, including the extraction fluids used in the Toxicity Characteristic Leaching Procedure (TCLP) of the United States Environmental Protection Agency (US EPA). The sorption results showed that the apatite was very effective in retaining Pb and was moderately effective in attenuating Cd and Zn at pH 4–5. Approximately 100% of the Pb applied was removed from solutions, representing a capacity of 151 mg of Pb/g of apatite, while 49% of Cd and 29% of Zn added were attenuated, with removal capacities of 73 and 41 mg g-1, respectively. The desorption experiments showed that the sorbed Pb stayed intact where only 14–23% and 7–14% of the sorbed Cd and Zn, respectively, were mobilized by the TCLP solutions. The apatite was also effective in removing dissolved Pb, Cd, and Zn leached from the contaminated soil using pH 3–12 solutions by 62.3–99.9, 20–97.9, and 28.6–98.7%, respectively. In particular, the apatite was able to reduce the metal concentrations in the TCLP-extracted soil leachates to below US EPA maximum allowable levels, suggesting that apatite could be used as a cost-effective option to remediating metal-contaminated soils, wastes, and/or water. The sorption mechanisms are variable in the reactions between the apatite and dissolved Pb, Cd, and Zn. The Pb removals primarily resulted from the dissolution of the apatite followed by the precipitation of hydroxyl fluoropyromorphite. Minor otavite precipitation was observed in the interaction of the apatite with aqueous Cd, but other sorption mechanisms, such as surface complexation, ion exchange, and the formation of amorphous solids, are primarily responsible for the removal of Zn and Cd.

Solvent-assisted proton transfer in catalysis by zeolite solid acids

Abstract: Intermolecular proton transfer in the gas phase is usually strongly disfavoured because the charged products are highly unstable. It is promoted in aqueous solution, however, because the high dielectric constant (e = 78.3) of water allows efficient stabilization of the corresponding cations and anions. Zeolites—microporous catalysts used in petroleum refining and the synthesis of chemical feedstocks—provide another medium for proton-transfer reactions1,2,3, because their anionic aluminosilicate frameworks are highly acidic. The low dielectric constant of zeolites (e ≈ 1.6; ref. 3) suggests, however, that such processes in the zeolite channels should involve concerted action rather than strong charge separation, and thus resemble gas-phase reactions. Here we demonstrate that solution-like proton-transfer behaviour can be induced in zeolites. We find that the co-injection of nitromethane into a catalytic flow reactor clearly enhances the conversion of methanol, isopropanol and acetone over the zeolite catalyst HZSM-5. Conservation of nitromethane during the course of reaction and its effects on the reactant–zeolite interaction complex seen by solid-state NMR indicate that nitromethane behaves in a manner similar to polar solvents: it promotes proton transfer by stabilizing ion-pair structures. These findings suggest that rationally selected solvents might provide a simple means to increase the efficiency of these industrially important catalysts.

Processing and Electrical Properties of Alkaline Earth‐Doped Lanthanum Gallate

Abstract: Oxides exhibiting substantial oxygen ion conductivity are utilized in a number of high-temperature applications, including solid oxide fuel cells, oxygen separation membranes, membrane reactors, and oxygen sensors Alkaline earth-doped lanthanum gallate powders were prepared by glycine/nitrate combustion synthesis Compacts of powders synthesized under fuel-rich conditions were sintered to densities greater than 97% of theoretical Appropriate doping with Sr or Ba on the A-site of the perovskite structure, and Mg on the B-site, resulted in oxygen ion conductivity higher than that of yttria-stabilized zirconia (YSZ), and high ionic transference numbers Doping with Ca and Mg resulted in lower conductivity than YSZ Thermal expansion coefficients of the doped gallates were higher than that of YSZ

High‐altitude energy source(s) for stable auroral red arcs

Abstract: Stable auroral red (SAR) arcs have been viewed across the midlatitude night sky with interest since their discovery in 1956. This relatively late discovery (compared to the poleward aurora) is a direct consequence of the subvisual levels of the delicate and diffuse light that makes up the SAR arc. Except in rare instances when the emissions actually crossover the threshold to visible levels, optical instruments are required to register their presence and document their morphology and occurrence frequency. SAR arcs are seen as relatively featureless, slowly changing bands of red light that can extend across the entire night sky. Early observations from the ground and from satellites established the relationship between SAR arcs and magnetic disturbances in near-Earth space involving the ring current (a population of high-energy ions trapped in the Earth's magnetic field). The long-lived, soft, red glow of SAR arcs reflects the slow energy loss from the ring current ions as they bounce back and forth in the Earth's confining field geometry, but the exact sequence of physical processes that feed a portion of the ring current energy to the SAR arc region is a matter of continuing debate. The midlatitude location of the SAR arc bands mirrors the high-altitude location of the outer portion of the ring current torus, but exactly how this positioning is related to gradients or enhancements in the high-altitude extension of the cold ionospheric plasma remained an open question. Our knowledge of SAR arcs and associated signatures now spans more than two full solar cycles. Detailed observations of the high-altitude space environment overlying the SAR arc region have been made, indicating that heavy ions from the lower atmosphere, energized by the solar wind interaction with the magnetosphere, play an important role in the SAR arc process. Sophisticated models of the coupled high- and low-altitude regions, involved in SAR arc formation, paint an interesting picture of the flow of energy between the atmosphere and near-Earth space. This energy flow culminates in the SAR arc's glowing red bands, which act, in turn, as sensitive markers of the interaction regions and processes. This emerging view of the SAR arc process and the new observational information that provided the underpinnings of its development from a rich framework of past theoretical and observational work is the subject of the present review.

Polycaprolactone/glass bioabsorbable implant in a rabbit humerus fracture model.

Abstract: Research in improved materials and methods for internal fixation has centered on internal fixators made of bioabsorbable materials such as polylactic acid, polyglycolic acid, and polyparadioxanone. These materials have two problems: the first is a postoperative complication related to a delayed inflammatory response; and the second is low strength characteristics. An alternative material developed to alleviate these problems is a composite of phosphate glass fibers embedded in the polymer polycaprolactone, referred to as PCL. In this study, intramedullary pins made of PCL were compared to stainless steel pins in a rabbit humerus osteotomy model. Specimens were harvested at 0, 6, and 12 weeks postoperatively, radiographs and mechanical testing to failure were performed at each time interval, and tissue was examined microscopically at 6 and 12 weeks. Histologic results showed PCL pins to be well tolerated with minimal inflammation around the pin. Mechanical testing revealed the PCL fixation to be weaker initially than the stainless steel fixation. There was significant stress shielding of stainless-steel-healed rabbit humeri when compared to the PCL/bone humeri. All osteotomies immobilized with PCL healed with abundant periosteal callus production. © 1997 John Wiley & Sons, Inc. J Biomed Mater Res, 36, 536–541, 1997.

Interference of locally excited surface plasmons

Abstract: Surface plasmon interactions on a finite silver layer are theoretically investigated using a coupled dipole formalism. The studied system consists of several protruding particles located on the surface of the layer that are scanned with an optical probe. An optical scan-image of the silver surface is obtained by assigning the recorded far-field radiation to the momentary position of the optical probe. Both, probe and protrusions are considered as single dipolar particles. Interferences of the locally excited surface plasmons can be recorded by detecting the radiation emitted into the lower half-space at angles beyond the critical angle of total internal reflection (forbidden light). The resulting scan images show excellent agreement with recent experimental measurements. The theory of the coupled dipole formalism using Green’s functions of a layered reference system is outlined and electromagnetic properties of surface plasmons are discussed.

Lithoautotrophy in the subsurface

Abstract: If microorganisms can carry out primary production within the Earth's crust, then the biosphere might not be totally dependent on surface-based photosynthesis. Potential chemical energy from purely geochemical sources within the earth can support growth of a number of known microorganisms, chiefly strict anaerobes, such as methanogens, homoacetogens, and sulfate-reducers. (Chemo)lithoautotrophic microorganisms have been detected in sedimentary systems, but they have not been shown to carry out primary production in situ, at least not without some dependence on surface-based photosynthesis. Microbial communities within igneous rock formations might, of necessity, be based on in situ primary production. Evidence has emerged for the presence of microorganism in basalt below the sea floor, but data on in situ activity are not yet in hand. Microbial communities have been observed, within continental flood basalts and granitic plutons, which appear to be based on in situ primary production by anaerobic bacteria. Geochemical measurements have confirmed that in situ activity is lithoautotrophic. This evidence for subsurface lithoautotrophic microbial ecosystems, which are not dependent on surface organisms, may have profound implications for life on the early Earth, and on other planets, including Mars.

Liquid Fuels by Low-Severity Hydrotreating of Biocrude

Abstract: Bio crude (fast pyrolysis oil from wood) was hydrotreated to minimize the negative aspects of this fuel. The instability of the oil was reduced by reaction of the most unstable functional groups. Concurrently, the oxygenated component of the oil was also reduced, resulting in an improved energy density. Changes in the physical handling properties were also modified. All of this change was accomplished at less severe processing conditions (lower temperature, shorter residence time) than that required for the earlier processing for gasoline production. Improved conversion was achieved by the use of a downflow reactor system. The experiments reported include those performed with clean (filtered hot vapor) biocrude just recently available from processing systems in the U.S.

Keeping an eye on power system dynamics

Abstract: The authors describe how the Bonneville Power Authority (USA) began to develop integrated monitoring and analysis tools to meet the need for accurate and coordinated dynamic power system information in 1990. They detail how the Dynamic Information Technology Package (DITPak) has evolved and how it now includes virtual instrumentation using LabVIEW software, modular and readily networked measurement hardware, streamlined analysis software in a MATLAB working environment and optional use of familiar workstation tools for display and report generation.