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At least 163 records · Page 9

Investigation of Polar Stratospheric Cloud Solid Particle Formation Mechanisms Using ILAS and AVHRR Observations in the Arctic

Satellite observations of denitrification and ice clouds in the Arctic lower stratosphere in February 1997 are used with Lagrangian microphysical box model calculations to evaluate nucleation mechanisms of solid polar stratospheric cloud (PSC) particles. The occurrences of ice clouds are not correlated in time and space with the locations of back trajectories of denitrified air masses, indicating that ice particle surfaces are not always a prerequisite for the formation of solid PSCs that lead to denitrification. In contrast, the model calculations incorporating a pseudoheterogeneous freezing process occurring at the vapor-liquid interface can quantitatively explain most of the observed denitrification when the nucleation activation free energy for nitric acid dihydrate formation is raised by only approx.10% relative to the current published values. Once nucleated, the conversion of nitric acid dihydrate to the stable trihydrate phase brings the computed levels of denitrification closer to the measurements. INDEX TERMS: 0305 Atmospheric Composition and Structure: Aerosols and particles (0345, 4801); 0320 Atmospheric Composition and Sb~lctureC: loud physics and chemistry; 0340 Atmospheric Composition and Structure: Middle atmosphere-composition and chemistry

Irie, H.↗

Bio-Organic Nanotechnology: Using Proteins and Synthetic Polymers for Nanoscale Devices

While the ability of proteins to self-assemble makes them powerful tools in nanotechnology, in biological systems protein-based structures ultimately depend on the context in which they form. We combine the self-assembling properties of synthetic diblock copolymers and proteins to construct intricately ordered, three-dimensional polymer protein structures with the ultimate goal of forming nano-scale devices. This hybrid approach takes advantage of the capabilities of organic polymer chemistry to build ordered structures and the capabilities of genetic engineering to create proteins that are selective for inorganic or organic substrates. Here, microphase-separated block copolymers coupled with genetically engineered heat shock proteins are used to produce nano-scale patterning that maximizes the potential for both increased structural complexity and integrity.

Molnar, Linda K.↗

The effects of complex chemistry on triple flames

The structure, ignition, and stabilization mechanisms for a methanol (CH3OH)-air triple flame are studied using Direct Numerical Simulations (DNS). The methanol (CH3OH)-air triple flame is found to burn with an asymmetric shape due to the different chemical and transport processes characterizing the mixture. The excess fuel, methanol (CH3OH), on the rich premixed flame branch is replaced by more stable fuels CO and H2, which burn at the diffusion flame. On the lean premixed flame side, a higher concentration of O2 leaks through to the diffusion flame. The general structure of the triple point features the contribution of both differential diffusion of radicals and heat. A mixture fraction-temperature phase plane description of the triple flame structure is proposed to highlight some interesting features in partially premixed combustion. The effects of differential diffusion at the triple point add to the contribution of hydrodynamic effects in the stabilization of the triple flame. Differential diffusion effects are measured using two methods: a direct computation using diffusion velocities and an indirect computation based on the difference between the normalized mixture fractions of C and H. The mixture fraction approach does not clearly identify the effects of differential diffusion, in particular at the curved triple point, because of ambiguities in the contribution of carbon and hydrogen atoms' carrying species.

Echekki, T.↗

Organic Chemistry in Space

Astronomical observations, theoretical modeling, laboratory simulation and analysis of extraterrestrial material have enhanced our knowledge of the inventory of organic matter in the interstellar medium (ISM) and on small bodies such as comets and asteroids (Ehrenfreund & Charnley 2000). Comets, asteroids and their fragments, meteorites and interplanetary dust particles (IDPs), contributed significant amounts of extraterrestrial organic matter to the young Earth. This material degraded and reacted in a terrestrial prebiotic chemistry to form organic structures that may have served as building blocks for life on the early Earth. In this talk I will summarize our current understanding of the organic composition and chemistry of interstellar clouds. Molecules of astrobiological relevance include the building blocks of our genetic material: nucleic acids, composed of subunits such as N-heterocycles (purines and pyrimidines), sugars and amino acids. Signatures indicative of inheritance of pristine and modified interstellar material in comets and meteorites will also be discussed.

Charnley, Steven↗

Method for Impeding Degradation of Porous Silicon Structures

This invention relates to surface modification of porosified silicon (pSi) structures with poly(alkylene) glycols for the purpose of controlled degradation of the silicon matrix and tailored release of encapsulated substances for biomedical applications. The pSi structures are currently used in diverse biomedical applications including bio-molecular screening, optical bio-sensoring, and drug delivery by means of injectable/orally administered carriers and implantable devices. The size of the pores and the surface chemistry of the pSi structure can be controlled during the microfabrication process and thereafter. A fine regulation of the degradation kinetics of mesoporous silicon structures is of fundamental importance. Polyethylene glycols (PEGs) represent the major category of surface modifying agents used in classical drug delivery systems and in pharmaceutical dosage forms. PEGylation enables avoidance of RES uptake, thus prolonging circulation time of intravenously injectable nanovectors. PEG molecules demonstrate little toxicity and immunogenicity, and are cleared from the body through the urine (molecular weight, MW less than 30 kDa) or in the feces (MW greater than 30kDa). The invention focuses on the possibility of finely tuning the degradation kinetics of the pSi nanovectors and other structures through surface conjugation of PEGs with various backbone lengths/MWs. To prove the concept, pSi nanovectors were covalently conjugated to seven PEGs with MW from 245 to 5,000 Da and their degradation kinetics in physiologically relevant media (phosphate buffer saline, PBS pH7.4, and fetal bovine serum) was assessed by the elemental analysis of the Si using inductive coupled plasma atomic emission spectroscopy (ICP-AES). The conjugation of the PEG with lowest MW to the nanovectors surface did not induce any change in the degradation kinetics in serum, but inhibited degradation and consequently the release of orthosilicic acid into buffer. When PEGs with the longer chains were evaluated, Si mass loss from the nanovectors was slowed down, and the PEGylated structures were almost fully degraded within 18 24 hours in serum and within 48 hours in PBS. The most dramatic effect was observed for high MW PEGs 3,400 and 5,000 Da, which prominently inhibited the degradation of the systems, with complete degradation achieved only after four days. For these PEGs, during the early stages of the degradation, there was a lag period of little or no Si mass loss from the nanovector. The obtained profiles were in agreement with the erosion of the nanovector surface as observed by scanning electron microscopy.

Vilentchouk, Biana Godin↗

The features of self-assembling organic bilayers important to the formation of anisotropic inorganic materials in microgravity conditions

Materials with directional properties are opening new horizons in a variety of applications including chemistry, electronics, and optics. Structural, optical, and electrical properties can be greatly augmented by the fabrication of composite materials with anisotropic microstructures or with anisotropic particles uniformly dispersed in an isotropic matrix. Examples include structural composites, magnetic and optical recording media, photographic film, certain metal and ceramic alloys, and display technologies including flat panel displays. The new applications and the need for model particles in scientific investigations are rapidly out-distancing the ability to synthesize anisotropic particles with specific chemistries and narrowly distributed physical characteristics (e.g. size distribution, shape, and aspect ratio).

Talham, Daniel R.↗

Effects of Rhenium Addition on the Temporal Evolution of the Nanostructure and Chemistry of a Model Ni-Cr-Al Superalloy: Experimental Observations - 1

The temporal evolution of the nanostructure and chemistry of a model Ni-8.5 at.% Cr-10 at. % Al alloy, with the addition of 2 at.% Re, aged at 1073 K from 0.25 to 264 h, was studied. Transmission electron microscopy and atom-probe tomography were used to measure the number density and mean radius of the gamma prime (L1(sub 2) structure)-precipitates and the chemistry of the gamma prime-precipitates and the gamma (face-centered cubic)-matrix, including the partitioning behavior of all alloying elements between the gamma- and gamma prime-phases and the segregation behavior at gamma/gamma prime interfaces. The precipitates remained spheroidal for an aging time of up to 264 h and, unlike commercial nickel-based superalloys containing Re, there was not confined (nonmonotonic) Re segregation at the gamma/gamma prime interfaces.

Yoon, Kevin E.↗

Structure of turbulent non-premixed flames modeled with two-step chemistry

Direct numerical simulations of turbulent diffusion flames modeled with finite-rate, two-step chemistry, A + B yields I, A + I yields P, were carried out. A detailed analysis of the turbulent flame structure reveals the complex nature of the penetration of various reactive species across two reaction zones in mixture fraction space. Due to this two zone structure, these flames were found to be robust, resisting extinction over the parameter ranges investigated. As in single-step computations, mixture fraction dissipation rate and the mixture fraction were found to be statistically correlated. Simulations involving unequal molecular diffusivities suggest that the small scale mixing process and, hence, the turbulent flame structure is sensitive to the Schmidt number.

Chen, J. H.↗

P-polarized reflectance spectroscopy: A high sensitive real-time monitoring technique to study surface kinetics under steady state epitaxial deposition conditions

This paper describes the results of real-time optical monitoring of epitaxial growth processes by p-polarized reflectance spectroscopy (PRS) using a single wavelength application under pulsed chemical beam epitaxy (PCBE) condition. The high surface sensitivity of PRS allows the monitoring of submonolayer precursors coverage on the surface as shown for GaP homoepitaxy and GaP on Si heteroepitaxy as examples. In the case of heteroepitaxy, the growth rate and optical properties are revealed by PRS using interference oscillations as they occur during growth. Super-imposed on these interference oscillations, the PRS signal exhibits a fine structure caused by the periodic alteration of the surface chemistry by the pulsed supply of chemical precursors. This fine structure is modeled under conditions where the surface chemistry cycles between phosphorus supersaturated and phosphorus depleted surfaces. The mathematical model describes the fine structure using a surface layer that increases during the tertiarybutyl phosphine (TBP) supply and decreases during and after the triethylgallium (TEG) pulse, which increases the growing GaP film thickness. The imaginary part of the dielectric function of the surface layer is revealed from the turning points in the fine structure, where the optical response to the first precursor pulse in the cycle sequence changes sign. The amplitude of the fine structure is determined by the surface layer thickness and the complex dielectric functions for the surface layer with the underlying bulk film. Surface kinetic data can be obtained by analyzing the rise and decay transients of the fine structure.

Dietz, Nikolaus↗

A comparative study of prebiotic and present day translational models

It is generally recognized that the understanding of the molecular basis of primitive translation is a fundamental step in developing a theory of the origin of life. However, even in modern molecular biology, the mechanism for the decoding of messenger RNA triplet codons into an amino acid sequence of a protein on the ribosome is understood incompletely. Most of the proposed models for prebiotic translation lack, not only experimental support, but also a careful theoretical scrutiny of their compatibility with well understood stereochemical and energetic principles of nucleic acid structure, molecular recognition principles, and the chemistry of peptide bond formation. Present studies are concerned with comparative structural modelling and mechanistic simulation of the decoding apparatus ranging from those proposed for prebiotic conditions to the ones involved in modern biology. Any primitive decoding machinery based on nucleic acids and proteins, and most likely the modern day system, has to satisfy certain geometrical constraints. The charged amino acyl and the peptidyl termini of successive adaptors have to be adjacent in space in order to satisfy the stereochemical requirements for amide bond formation. Simultaneously, the same adaptors have to recognize successive codons on the messenger. This translational complex has to be realized by components that obey nucleic acid conformational principles, stabilities, and specificities. This generalized condition greatly restricts the number of acceptable adaptor structures.

Rein, R.↗

Civil propulsion technology for the next twenty-five years

The next twenty-five years will see major advances in civil propulsion technology that will result in completely new aircraft systems for domestic, international, commuter and high-speed transports. These aircraft will include advanced aerodynamic, structural, and avionic technologies resulting in major new system capabilities and economic improvements. Propulsion technologies will include high-speed turboprops in the near term, very high bypass ratio turbofans, high efficiency small engines and advanced cycles utilizing high temperature materials for high-speed propulsion. Key fundamental enabling technologies include increased temperature capability and advanced design methods. Increased temperature capability will be based on improved composite materials such as metal matrix, intermetallics, ceramics, and carbon/carbon as well as advanced heat transfer techniques. Advanced design methods will make use of advances in internal computational fluid mechanics, reacting flow computation, computational structural mechanics and computational chemistry. The combination of advanced enabling technologies, new propulsion concepts and advanced control approaches will provide major improvements in civil aircraft.

Rosen, Robert↗

Copper-containing ceramic precursor synthesis: Solid-state transformations and materials technology

Three copper systems with relevance to materials technology are discussed. In the first, a CuS precursor, Cu4S1O (4-methylpyridine)(sub 4)- (4-MePy), was prepared by three routes: reaction of Cu2S, reaction of CuBr-SMe2, and oxidation of copper powder with excess sulfur in 4-methylpyridine by sulfur. In the second, copper powder was found to react with excess thiourea (H2NC(S)NH2) in 4-methylpyridine to produce thiocyanate (NCS(-)) complexes. Three isolated and characterized compounds are: Cu(NCS)(4-MePy)(sub 2), a polymer, (4-MePy-H)(Cu(NCS)(sub 3)(4-MePy)(sub 2)), a salt, and t-Cu(NCS)(sub 2)(4-MePy)(sub 4). Finally, an attempt to produce a mixed-metal sulfide precursor of Cu and Ga in N-methylimidazole (N-MeIm) resulted in the synthesis of a Cu-containing polymer, Cu(SO4)(N-MeIm). The structures are presented; the chemistry will be briefly discussed in the context of preparation and processing of copper-containing materials for aerospace applications.

Hepp, Aloysius F.↗

A detailed evaluation of heating processes in the middle atmosphere

A fundamental problem in the study of the terrestrial middle atmosphere is to calculate accurately the local heating due to the absorption of solar radiation. Knowledge of the heat budget is essential to understanding the atmospheric thermal structure, atmospheric motions, atmospheric chemistry, and their coupling. The evaluation of heating rates is complicated (especially above the stratopause) by the fact that the heating is not a simple one-step process. That is, the absorbed solar energy does not all immediately appear as heat. Rather, substantial portions of the incident energy may appear as internal energy of excited photolysis products (e.g., O(1D) or O2(1 delta)) or as chemical potential energy of product species such as atomic oxygen. The ultimate disposition of the internal and chemical energy possessed by the photolysis products determines the efficiency and thus the rate at which the middle atmosphere is heated. In studies of the heat budget, it is also vitally important to consider transport of long lived chemical species such as atomic oxygen above approximately 80 km. In such cases, the chemical potential energy may be transported great distances (horizontally or vertically) before undergoing a reaction to release the heat. Atomic oxygen influences the heating not only by reactions with itself and with O2 but also by reactions with odd-hydrogen species, especially those involving OH (Mlynczak and Solomon, 1991a). Consequently, absorbed solar energy may finally by converted to heat a long time after and at a location far from the original deposition. The purpose of this paper is to examine the solar and chemical heating processes and to present parameterizations for the heating efficiencies readily applicable for use in numerical models and heat budget studies. In the next two sections the processes relevant to the heating efficiencies for ozone and molecular oxygen will be reviewed. In section 4 the processes for the exothermic reactions will be reviewed and parameterizations for the heating efficiencies for both the solar and chemical processes will be presented in Section 5.

Mlynczak, Martin↗

Cellular control lies in the balance of forces

Mechanical tension generated within the cytoskeleton of living cells is emerging as a critical regulator of biological function in diverse situations ranging from the control of chromosome movement to the morphogenesis of the vertebrate brain. In this article, we review recent advances that have been made in terms of understanding how cells generate, transmit and sense mechanical tension, as well as how they use these forces to control their shape and behavior. An integrated view of cell regulation that incorporates mechanics and structure as well as chemistry is beginning to emerge.

Review, Tutorial↗

Space Applications of Polymeric Materials

Polymers constitute an extremely large class of materials generally based on carbon chemistry. Their long chain structures and unique molecular architecture make them distinct from metals and ceramics and provided them with a very wide range of properties.

Polymer Outgassing radiation composites inflatable↗

Initial Observations by the Mars Exploration Rover Opportunity at Cape York, Meridiani Planum

Since the beginning of its mission, the MER rover Opportunity has visited a sequence of progressively larger impact craters in order to characterize rocks that represent an ever broader stratigraphic range. Endeavour Crater is by far the largest crater that this rover has visited, therefore the crater rim provides materials from strata that are much deeper and older than any materials yet sampled. Indeed, the Mars Reconnaissance Orbiter CRISM instrument detected spectral signatures of hydrated phyllosilicates in several rim segments, consistent with a Noachian provenance. In addition, the crater rim might have recorded the effects of the original impact as well as the thermal processes that occurred in its aftermath. This report summarizes initial observations of geologic structures and the fabrics, chemistry and mineralogy of rocks. Cape York is an N/NE - S/SW-trending segment of crater rim that is bounded by rim segments that are more deeply eroded, forming embayments. Opportunity drove onto the southwest margin of Cape York and has traversed across the Cape to a ridge near its northern end. The rim of Endeavour Crater was severely degraded and then on lapped by Meridiani sulfate-rich deposits, indicating that Cape York deposits experienced extensive erosion prior to the deposition of Meridiani Planum sulfate-rich sediments. Cape York consists of impact-uplifted rocks that are surrounded by a younger bedrock bench that might represent sediments shed from Cape York. The uplifted rock "Tisdale-2," located near the southern end of Cape York, is a polymict lithic breccia. Its elemental composition resembles a mixture of basalt plus bedrock encountered previously at Meridiani Planum, and it is relatively enriched in Ni, Zn, P, characteristic of hydrothermal fluids. "Chester Lake" and "Greeley Haven" are bedrock surfaces located near the southern and northern ends of Cape York, respectively, and they exhibit fabrics reminiscent of suevites. The rocks that were analyzed so far are quite different from any rocks previously encountered by Opportunity and Spirit. Several light-toned vein deposits (approx 1 cm) were discovered in the bench that borders the western flanks of Cape York. The vein "Homestake" is rich in Ca and S, and it exhibits a spectral feature near 1000 run caused by hydration, indicating that "Homestake" consists substantially of gypsum. The relationship(s) between these veins and the sulfate-rich layered deposits at Meridiani Planum remains uncertain. The veins might have been deposited by sulfate-rich fluids perhaps either in the immediate aftermath of the impact that formed Endeavour Crater or at some later time. Current uncertainties notwithstanding, the novel lithologies at Cape York are significantly older than the sulfate-rich sedimentary rocks at Meridiani Planum, and these lithologies have recorded episodes of aqueous activity from earlier epochs, perhaps during the Noachian. The author acknowledges the contributions of the Athena Science Team, the MER engineering team, JPL and NASA.

Marais, David J.↗