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Monte Carlo Simulation of Endlinking Oligomers

This report describes initial efforts to model the endlinking reaction of phenylethynyl-terminated oligomers. Several different molecular weights were simulated using the Bond Fluctuation Monte Carlo technique on a 20 x 20 x 20 unit lattice with periodic boundary conditions. After a monodisperse "melt" was equilibrated, chain ends were linked whenever they came within the allowed bond distance. Ends remained reactive throughout, so that multiple links were permitted. Even under these very liberal crosslinking assumptions, geometrical factors limited the degree of crosslinking. Average crosslink functionalities were 2.3 to 2.6; surprisingly, they did not depend strongly on the chain length. These results agreed well with the degrees of crosslinking inferred from experiment in a cured phenylethynyl-terminated polyimide oligomer.

Hinkley, Jeffrey A.↗

Modeling the Growth Rates of Tetragonal Lysozyme Crystal Faces

The measured macroscopic growth rates of the (110) and (101) faces of tetragonal lysozyme show an unexpectedly complex dependence on the supersaturation. The growth rates decay asymptotically to zero when the supersaturation is lowered to zero and increase rapidly when the supersaturation is increased. When supersaturations are increased still further the growth rates attain a maximum before starting to decrease. However, growth of these crystals is known to proceed by the classical dislocation and 2D nucleation growth mechanisms. This anomaly can be explained if growth is assumed to occur not by monomer units but by lysozyme aggregates. Analysis of the molecular packing of these crystals revealed that they were constructed of strongly bonded 4(sub 3) helices, while weaker bonds were responsible for binding the helices to each other. It follows that during crystal growth the stronger bonds are formed before the weaker ones. Thus, the growth of these crystals could be viewed as a two step process: aggregate growth units corresponding to the 4(sub 3) helix are first formed in the bulk solution by stronger intermolecular bonds and then attached to the crystal face by weaker bonds on dislocation hillocks or 2D islands. This will lead to a distribution of aggregates in the solution with monomers and lower order aggregates being predominant at low supersaturations and higher order aggregates being predominant at high supersaturations. If the crystal grows mostly by higher order aggregates, such as tetramers and octamers, it would explain the anomalous dependence of the growth rates on the supersaturation. Besides the analysis of molecular packing, a comprehensive analysis of the measured (110) and (101) growth rates was also undertaken in this study. The distribution of aggregates in lysozyme nutrient solutions at various solution conditions were determined from reversible aggregation reactions at equilibrium. The supersaturation was defined for each aggregate species with respect to its concentration at saturation in order to apply growth rate models to this process. The measured growth rates were then compared with the predicted ones from several dislocation and 2D nucleation growth models, employing tetramer and octamer growth units in polydisperse solutions and monomer units in monodisperse solutions. For the (110) face, the calculations consistently showed that the measured growth rates followed the expected model relations with octamer growth units. For the (101) face, it is not possible to obtain a clear agreement between the predicted and measured growth rates for a single growth unit as done for the (110) face. However, the calculations do indicate that the average size of the growth unit is between a tetramer and an octamer. This suggests that tetramers, octamers and other intermediate size growth units all participate in the growth process for this face. These calculations show that it is possible to model the macroscopic protein crystal growth rates if the molecular level processes can be account for, particularly protein aggregation processes in the bulk solution. Our recent investigations of tetragonal lysozyme crystals employing high resolution atomic force microscopy scans have further confirmed the growth of these crystals by aggregate growth units corresponding to 4(sub 3) helices.

Li, Meirong↗

The Features of Self-Assembling Organic Bilayers Important to the Formation of Anisotropic Inorganic Materials in Microgravity Conditions

There is a growing need for inorganic anisotropic particles in a variety of materials science applications. 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. While considerable progress has been made toward developing an understanding of the synthesis of powders composed of monodispersed, spherical particles, these efforts have not been transferred to the synthesis of anisotropic nanoparticles. The major objective of the program is to develop a fundamental understanding of the growth of anisotropic particles at organic templates, with emphasis on the chemical and structural aspects of layered organic assemblies that contribute to the formation of anisotropic inorganic particles.

Talham, Daniel R.↗

Theory of Dust Voids in Plasmas

Dusty plasmas in a gas discharge often feature a stable void, i.e., a dust-free region inside the dust cloud. This occurs under conditions relevant to both plasma processing discharges and plasma crystal experiments. The void results from a balance of the electrostatic and ion drag forces on a dust particle. The ion drag force is driven by a flow of ions outward from an ionization source and toward the surrounding dust cloud, which has a negative space charge. In equilibrium the force balance for dust particles requires that the boundary with the dust cloud be sharp, provided that the particles are cold and monodispersive. Numerical solutions of the one-dimensional nonlinear fluid equations are carried out including dust charging and dust-neutral collisions, but not ion-neutral collisions. The regions of parameter space that allow stable void equilibria are identified. There is a minimum ionization rate that can sustain a void. Spatial profiles of plasma parameters in the void are reported. In the absence of ion-neutral collisions, the ion flow enters the dust cloud's edge at Mach number M = 1. Phase diagrams for expanding or contracting voids reveal a stationary point corresponding to a single stable equilibrium void size, provided the ionization rate is constant. Large voids contract and small voids expand until they attain this stationary void size. On the other hand, if the ionization rate is not constant, the void size can oscillate. Results are compared to recent laboratory and microgravity experiments.

Goree, J.↗

"Electrostructural Phase Changes" In Charged Particulate Clouds: Planetary and Astrophysical Implications

There is empirical evidence that freely-suspended triboelectrostatically charged particulate clouds of dielectric materials undergo rapid conversion from (nominally) monodispersed "aerosols" to a system of well-defined grain aggregates after grain motion or fluid turbulence ceases within the cloud. In United States Microgravity Laboratory Space Shuttle experiments USML-1 and USML-2, it was found that ballistically-energized grain dispersions would rapidly convert into populations of filamentary aggregates after natural fluid (air) damping of grain motion. Unless continuously disrupted mechanically, it was impossible to maintain a non-aggregated state for the grain clouds of sand-size materials. Similarly, ground- based experiments with very fine dust-size material produced the same results: rapid, impulsive "collapse" of the dispersed grains into well-defined filamentary structures. In both ground-based and microgravity experiments, the chains or filaments were created by long-range dipole electrostatic forces and dipole-induced dielectric interactions, not by monopole interactions. Maintenance of the structures was assisted by short-range static boundary adhesion forces and van der Waals interactions. When the aggregate containers in the USML experiments were disturbed after aggregate formation, the quiescently disposed filaments would rearrange themselves into fractal bundles and tighter clusters as a result of enforced encounters with one another. The long-range dipole interactions that bring the grains together into aggregates are a product of randomly-distributed monopole charges on the grain surfaces. In computer simulations, it has been shown that when the force vectors of all the random charges (of both sign) on a grain are resolved mathematically by assuming Coulombic interaction between them, the net result is a dipole moment on individual grains, even though the grains are electrically neutral insofar as there is no predominance, on their surface, of one charge sign over another. The random charges of both sign derive from natural grain-to-grain interactions that produce triboelectrification via charge exchange every time grain surfaces make contact with one another. The conversion from a random distribution of grains (upon which there are randomly distributed charges) into an organization of electrostatically-ordered aggregates, can be regarded (within the framework of granular-material science) as an "electrical or Coulombic phase change" of the particulate cloud. It is not totally dissimilar from the more normal phase-change concept in which, for example, a gas with long free-path-molecules suddenly becomes a solid as a result of structural ordering of the molecules (notably, also the result of electronic forces, albeit at a different scale). In both the gas-to-solid case, and the aerosol-to-aggregate case, the same materials and charges are present before and after the phase change, but their arrangement now has a higher degree of order and a lower-energy configuration. An input of energy into the system is required to reverse the situation. The aggregates in the USML experiments were observed to undergo at least two phase changes as noted above. The point about phase changes, and by implication, the "electrostructural" reorganizations in particulate clouds, is the following: (a) they can occur very rapidly, almost spontaneously, above a critical cloud density, (b) in going from a higher energy state to a lower energy state, they convert to a denser system, (c) energy must be required to reverse the situation, implying that energy is released during the high-to-low energy phase change. In applying this information to natural particulate clouds, some inferences can be made (it is stressed that reference is still to dielectric materials attracted by dipole forces). There are several natural settings to which the USML observations apply, and to which the phase-change implications likewise apply. Dense clouds of triboelectrically-charged, kinetically-energized grains are to be found in volcanic eruptions (particularly on earth), aeolian dust storms (particularly on Mars), meteorite impact ejecta curtains (on all planets), in "immature" debris rings around planets (e.g., that from which our own Moon may have condensed), and in gravitationally collapsing protoplanetary dust/planetesimal debris disks where dielectric granules are being increasingly brought into collisional relationships with one another (increasing both charge exchange and physical proximity). It is noted that in many of these cases, the degree of electrical charging on the grains is likely to be much higher than that in the USML experiments where charging was not enhanced above the "normal", naturally encountered level for the particular materials (quartz, glass, and various silicate minerals). Application of the phase-change concept suggests that volcanic, aeolian, and impact debris clouds may, under certain circumstances, undergo rapid, impulsive, or even catastrophic collapse into a denser state that will lead to rapid precipitation or fall-out of suspended particulates. Although this idea has been suggested previously by the author , the phase change concept possibly permits some new insights into cloud-system behavior. For example, in a protoplanetary debris disk, the work of gravity may suddenly be enhanced by electrostatically driven collapse of the system when materials reach a critical intergranular spacing or grain number density. This might reduce the rate of planet formation by orders of magnitude (considering the ratio of g-forces to electrostatic ones for very small grains in close proximity), and indeed, it might drive the collapse into a system configuration that would perhaps not be created by gravity alone. Additional information is contained in the original.

Marshall, J. R.↗

Over-Expression, Purification and Crystallization of Human Dihydrolipoamide Dehydrogenase

Dehydrolipoamide dehydrogenase (E3; dihydrolipoan-tide:NAD+ oxidoreductase, EC 1.8.1.4) is a common catalytic component found in pyruvate dehydrogenase complex, alpha-ketoglutarate dehydrogenase complex, and branched-chain cc-keto acid dehydrogenase complex. E3 is also a component (referred to as L protein) of the glycine cleavage system in bacterial metabolism (2). Active E3 forms a homodimer with four distinctive subdomain structures (FAD binding, NAD+ binding, central and interface domains) with non-covalently but tightly bound FAD in the holoenzyme. Deduced amino acids from cloned full-length human E3 gene showed a total of 509 amino acids with a leader sequence (N-terminal 35 amino acids) that is excised (mature form) during transportation of expressed E3 into mitochondria membrane. So far, three-dimensional structure of human E3 has not been reported. Our effort to achieve the elucidation of the X-ray crystal structure of human E3 will be presented. Recombinant pPROEX-1 expression vector (from GIBCO BRL Life Technologies) having the human E3 gene without leader sequence was constructed by Polymerase Chain Reaction (PCR) and subsequent ligation, and cloned in E.coli XL1-Blue by transformation. Since pPROEX-1 vector has an internal His-tag (six histidine peptide) located at the upstream region of a multicloning site, one-step affinity purification of E3 using nickelnitriloacetic acid (Ni-NTA) agarose resin, which has a strong affinity to His-tag, was feasible. Also a seven-amino-acid spacer peptide and a recombinant tobacco etch virus protease recognition site (seven amino acids peptide) found between His-tag and first amino acid of expressed E3 facilitated the cleavage of His-tag from E3 after the affinity purification. By IPTG induction, ca. 15 mg of human E3 (mature form) was obtained from 1L LB culture with overnight incubation at 25C. Over 98% of purity of E3 from one-step Ni-NTA agarose affinity purification was confirmed by SDS-PAGE analysis. For crystallization, E3 samples were prepared with and without His-tag. To minimize the aggregation of E3, apo- and holo- forms of E3s were tested, as well as a mutated E3. Dynamic light scattering measurements revealed that the E3 preparations without His-tag and substrate are highly monodispersive with regard to homodimers. Consequent crystallization trials of this E3 preparation led to single crystals of E3 grown by the vapor diffusion method. Crystals were obtained within a few days from solution containing poly (ethylene glycol) monomethyl ether 5000 as a precipitant. Autoindexing and integration of the X-ray diffraction data showed that E3 crystals belong to an orthorhombic system with unit cell parameters a-- 123. 1, b= 165.3 and c=214.3A. Further optimization of protein preparation and crystallization experiments for the structural determination will be discussed.

Hong, Y. S.↗

Generation of Bubbly Suspensions in Low Gravity

Generation of a uniform monodisperse bubbly suspension in low gravity is a rather difficult task because bubbles do not detach as easily as on Earth. Under microgravity, the buoyancy force is not present to detach the bubbles as they are formed from the nozzles. One way to detach the bubbles is to establish a detaching force that helps their detachment from the orifice. The drag force, established by flowing a liquid in a cross or co-flow configuration with respect to the nozzle direction, provides this additional force and helps detach the bubbles as they are being formed. This paper is concerned with studying the generation of a bubbly suspension in low gravity in support of a flight definition experiment titled "Behavior of Rapidly Sheared Bubbly Suspension." Generation of a bubbly suspension, composed of 2 and 3 mm diameter bubbles with a standard deviation <10% of the bubble diameter, was identified as one of the most important engineering/science issues associated with the flight definition experiment. This paper summarizes the low gravity experiments that were conducted to explore various ways of making the suspension. Two approaches were investigated. The first was to generate the suspension via a chemical reaction between the continuous and dispersed phases using effervescent material, whereas the second considered the direct injection of air into the continuous phase. The results showed that the reaction method did not produce the desired bubble size distribution compared to the direct injection of bubbles. However, direct injection of air into the continuous phase (aqueous salt solution) resulted in uniform bubble-diameter distribution with acceptable bubble-diameter standard deviation.

Nahra, Henry K.↗

Extensional Flow of a Polystyrene Boger Fluid Through a 4:1:4 Axisymmetric Contraction/Expansion

The creeping flow of a dilute (0.025 wt%) monodisperse polystyrene/polystyrene Boger fluid through a 4:1:4 axisymmetric contraction/expansion is experimentally observed for a wide range of Deborah numbers. Pressure drop measurements across the orifice plate show a large extra pressure drop that increases monotonically with Deborah number above the value observed for a similar Newtonian fluid at the same flow rate. This enhancement in the dimensionless pressure drop is not associated with the onset of a flow instability, yet it is not predicted by existing steady-state or transient numerical computations with simple dumbbell models. It is conjectured that this extra pressure drop is the result of an additional dissipative contribution to the polymeric stress arising from a stress-conformation hysteresis in the strong non-homogeneous extensional flow near the contraction plane. Such a hysteresis has been independently measured and computed in recent studies of homogeneous transient uniaxial stretching of PS/PS Boger fluids. Flow visualization and velocity field measurements using digital particle image velocimetry (DPIV) show large upstream growth of the corner vortex with increasing Deborah number. At large Deborah numbers, the onset of an elastic instability is observed, first locally as small amplitude fluctuations in the pressure measurements, and then globally as an azimuthal precessing of the upstream corner vortex accompanied by periodic oscillations in the pressure drop across the orifice.

Rothstein, Jonathan P.↗

A Novel Acousto-Electric Levitator for Studies of Drop and Particle Clusters and Arrays

A novel and compact instrumentation for studying the behavior of drop sprays and of clusters of drops now permits fundamental research into the behavior of reacting and non-reacting fluid and solid species. The new capability is made possible by simultaneous acousto-electric levitation and charging of "seed" droplets (10-30 microns in diameter) which come together in 2-D clusters (with up to 300 droplets). These clusters are interesting in their own right because of their crystalline and quasi-crystalline forms, which depend on the acoustic and electric field parameters. By varying the electric and acoustic field intensities, one can cause a cluster of droplets to condense into larger drops (e.g. 50-300 microns) which, because of their charge, form uniformly spaced 2-D arrays of monodispersed drops (e.g. 30-40 array drops in preliminary experiments). One or more layers of these 2-D arrays can form in the acoustic standing wave. Such a configuration permits a wide range of fundamental studies of drop evaporation, combustion, and nucleation. The drops can be single or multicomponent. Therefore, fundamental materials studies can also be performed. Using this same Cluster and Array Generation (CAG) instrumentation, it has been also possible in preliminary experiments to demonstrate the clustering and arraying of solid particles, both coated with an electrically conducting layer and uncoated, and both charged and uncharged.

Tian, Yuren↗

Engineering of Novel Biocolloid Suspensions

Colloidal suspensions are materials with a variety of uses from cleaners and lubricants to food, cosmetics, and coatings. In addition, they can be used as a tool for testing the fundamental tenets of statistical physics. Colloidal suspensions can be synthesized from a wide variety of materials, and in the form of monodisperse particles, which can self-assemble into highly ordered colloidal crystal structures. As such they can also be used as templates for the construction of highly ordered materials. Materials design of colloids has, to date, relied on entropic self-assembly, where crystals form as result of lower free energy due to a transition to order. Here, our goal is to develop a completely new method for materials fabrication using colloidal precursors, in which the self-assembly of the ordered colloidal structures is driven by a highly controllable, attractive interaction. This will greatly increase the range of potential structures that can be fabricated with colloidal particles. In this work, we demonstrate that colloidal suspensions can be crosslinked through highly specific biological crosslinking reactions. In particular, the molecules we use are protein-carbohydrate interactions derived from the immune system. This different driving force for self-assembly will yield different and novel suspensions structures. Because the biological interactions are heterotypic (A binding to B), this chemical system can be used to make binary alloys in which the two colloid subpopulations vary in some property - size, density, volume fraction, magnetic susceptibility, etc. An additional feature of these molecules which is unique - even within the realm of biological recognition - is that the molecules bind reversibly on reasonable time-scales, which will enable the suspension to sample different configurations, and allow us to manipulate and measure the size of the suspension dynamically. Because of the wide variety of structures that can be made from these novel colloids, and because the suspension structure can be altered dynamically, we believe this biocolloid system will yield a novel set of materials with many technological applications, including sensors (both biological and non-biological), optical filters and separation media.

Hammer, D. A.↗

Electrophoretic Porosimetry of Sol-Gels

It has been hypothesized that gravity has an effect on the formation and resulting microstructure of sol-gels. In order to more clearly resolve the effect of gravity, pores may be non-destructively analyzed in the wet gel, circumventing the shrinkage and coarsening associated with the drying procedure. We discuss the development of an electrophoretic technique, analogous to affinity chromatography, for the determination of pore size distribution and its application to silica gels. Specifically a monodisperse charged dye is monitored by an optical densitometer as it moves through the wet gel under the influence of an electric field. The transmittance data (output) represents the convolution of the dye concentration profile at the beginning of the run (input) with the pore size distribution (transfer function), i.e. linear systems theory applies. Because of the practical difficulty in producing a delta function input dye profile we prefer instead to use a step function. Average pore size is then related to the velocity of this dye front, while the pore size distribution is related to the spreading of the front. Preliminary results of this electrophoretic porosimetry and its application to ground and space-grown samples will be discussed.

Snow, L. A.↗

Electrostatics of Granular Material (EGM): Space Station Experiment

Aggregates were observed to form very suddenly in a lab-contained dust cloud, transforming (within seconds) an opaque monodispersed cloud into a clear volume containing rapidly-settling, long hair-like aggregates. The implications of such a "phase change" led to a series of experiments progressing from the lab, to KC-135, followed by micro-g flights on USML-1 and USML-2, and now EGM slated for Space Station. We attribute the sudden "collapse" of a cloud to the effect of dipoles. This has significant ramifications for all types of cloud systems, and additionally implicates dipoles in the processes of cohesion and adhesion of granular matter. Notably, there is the inference that like-charged grains need not necessarily repel if they are close enough together: attraction or repulsion depends on intergranular distance (the dipole being more powerful at short range), and the D/M ratio for each grain, where D is the dipole moment and M is the net charge. We discovered that these ideas about dipoles, the likely pervasiveness of them in granular material, the significance of the D/M ratio, and the idea of mixed charges on individual grains resulting from tribological processes --are not universally recognized in electrostatics, granular material studies, and aerosol science, despite some early seminal work in the literature, and despite commercial applications of dipoles in such modern uses as "Krazy Glue", housecleaning dust cloths, and photocopying. The overarching goal of EGM is to empirically prove that (triboelectrically) charged dielectric grains of material have dipole moments that provide an "always attractive" intergranular force as a result of both positive and negative charges residing on the surfaces of individual grains. Microgravity is required for this experiment because sand grains can be suspended as a cloud for protracted periods, the grains are free to rotate to express their electrostatic character, and Coulombic forces are unmasked. Suspended grains will be "interrogated" by applied electrical fields. In one module, grains will be immersed in an inhomogeneous electric field and allowed to be attracted towards or repelled from the central electrode of the module: part of the grain's speed will be a function of its net charge (monopole), part will be a function of the dipole. Observed grain position vs. time will provide a curve that can be deconvolved into the dipole and monopole forces responsible, since both have distinctive radial dependencies. In a second approach, the inhomogeneous field will be alternated at low frequency (e.g., every 5-10 seconds) so that the grains are alternately attracted and repelled from the center of the field. The resulting "zigzag" grain motion will gradually drift inwards, then suddenly change to a unidirectional inward path when a critical radial distance is encountered (a sort of "Coulombic event horizon") at which the dipole strength supersedes the monopole strength --thus proving the presence of a dipole, while also quantifying the D/M ratio. In a second module, an homogeneous electric field eliminates dipole effects (both Coulombic and induced) to provide calibration of the monopole and to more readily evaluate net charge statistical variance. In both modules, the e-fields will be exponentially step-ramped in voltage during the experiment, so that the field "nominalizes" grain speed while spreading the response time --effectively forcing each grain to "wait its turn" to be measured. In addition to rigorously quantifying M, D, and the D/M ratio for many hundreds of grains, the experiment will also observe gross electrometric and RF discharge phenomena associated with grain activity. The parameter space will encompass grain charging levels (via intentional triboelectrification), grain size, cloud density, and material type. Results will prove or disprove the dipole hypothesis. In either case, light will be shed on the role of electrostatic forces in governing granular systems. Knowledge so gained can be applied to natural clouds such as protostellar and protoplanetary dust and debris systems, planetary rings, planetary dust palls and aerosols created by volcanic, impact, aeolian, firestorm, or nuclear winter processes. The data are also directly applicable to adhesion, cohesion, transport, dispersion, and collection of granular materials in industrial, agricultural, pharmaceutical applications, and in fields as diverse as dust contamination of space suits on Mars and crop spraying on Earth.

Marshall, J.↗

Electrophoretic Focusing

Electrophoretic focusing is a new method of continuous flow electrophoresis that introduces precision flow control to achieve high resolution separations. The electric field is applied perpendicular to an incoming sample lamina and buffer but also perpendicular to the broad faces of the thin rectangular chamber. A uniform fluid cross-flow then enters and exits the separation chamber through the same broad faces which are porous. A balance is achieved by adjusting either the electric field or the cross-flow so the desired sample fraction with its specific migration velocity encounters an opposing flow of the same velocity. Applying an electric field transverse to the incoming sample lamina and opposing this field with a carefully configured buffer flow, a sample constituent can be selected and focused into a narrow stream for subsequent analysis. Monotonically changing either electric field or buffer cross-flow will yield a scan of all constituents of the sample. Stopping the scan increases the collection time for minor constituents to improve their analysis. Using the high voltage gradients and/or cross-flow to rapidly deflect extraneous sample through the porous screens and into either of the side (purge) chambers, the selected sample is focused in the center plane of the separation chamber and collected without contact or interaction with the separation chamber walls. Results will be presented on the separation of a range of materials including dyes, proteins, and monodisperse polystyrene latexes. Sources of sample dispersion inherent in other electrokinetic techniques will be shown to be negligible for a variety of sample concentrations, buffer properties and operating conditions.

Snyder, Robert S.↗

Performance Evaluation of Particle Sampling Probes for Emission Measurements of Aircraft Jet Engines

Considerable attention has been recently received on the impact of aircraft-produced aerosols upon the global climate. Sampling particles directly from jet engines has been performed by different research groups in the U.S. and Europe. However, a large variation has been observed among published data on the conversion efficiency and emission indexes of jet engines. The variation results surely from the differences in test engine types, engine operation conditions, and environmental conditions. The other factor that could result in the observed variation is the performance of sampling probes used. Unfortunately, it is often neglected in the jet engine community. Particle losses during the sampling, transport, and dilution processes are often not discussed/considered in literatures. To address this issue, we evaluated the performance of one sampling probe by challenging it with monodisperse particles. A significant performance difference was observed on the sampling probe evaluated under different temperature conditions. Thermophoretic effect, nonisokinetic sampling and turbulence loss contribute to the loss of particles in sampling probes. The results of this study show that particle loss can be dramatic if the sampling probe is not well designed. Further, the result allows ones to recover the actual size distributions emitted from jet engines.

Lee, Poshin↗

A Model for Macromolecular Crystallization

Macromolecular crystallization is a complex process. involving a system which typically has 5 or more components (macromolecule, water, buffer + counter ion, and precipitant). Whereas small molecules have only several well defined contacts in the crystal lattice, macromolecules generally have 10's or even 100's of contacts between molecules. These can range from hydrogen bonds (direct or water-mediated), through van der Waals, hydrophobic, salt bridges, and ion-mediated contacts. The latter interactions are stronger and require some specificity in the molecular alignment, while the others are weaker, more prevalent, and more promiscuous, i.e., can often be readily broken and reformed between other sites. Formation of a consistent, ordered, 3D structure may be impossible in the absence of any or presence of too many strong interactions. Further complicating the process is the inherent structural asymmetry of monomeric single chain macromolecules. The process of crystal nucleation and growth involves the ordered assembly of growth units into a defined 3D lattice. We suggest that for many macromolecules, particularly those that are monomeric, this involves a preliminary solution-phase assembly process into a growth unit having some symmetry prior to addition to the lattice, recapitulating the initial stages of the nucleation process. If this model is correct then fluids and crystal growth models assuming a strictly monodisperse nutrient solution need to be revised. Experimental evidence, based upon face growth rate, AFM, and fluorescence energy transfer data, for a postulated model of the nucleation of tetragonal lysozyme crystals and how it transitions into crystal growth will be presented.

Pusey, Marc L.↗

A Model for Tetragonal Lysozyme Crystal Nucleation and Growth

Macromolecular crystallization is a complex process, involving a system that typically has 5 or more components (macromolecule, water, buffer + counter ion, and precipitant). Whereas small molecules have only a few contacts in the crystal lattice, macromolecules generally have 10's or even 100's of contacts between molecules. These can range from hydrogen bonds (direct or water-mediated), through van der Waals, hydrophobic, salt bridges, and ion-mediated contacts. The latter interactions are stronger and require some specificity in the molecular alignment, while the others are weaker, more prevalent, and more promiscuous, i.e., can be readily broken and reformed between other sites. Formation of a consistent, ordered, 3D structure may be difficult or impossible in the absence of any or presence of too many strong interactions. Further complicating the process is the inherent structural asymmetry of monomeric (single chain) macromolecules. The process of crystal nucleation and growth involves the ordered assembly of growth units into a defined 3D lattice. We suggest that for many macromolecules, particularly those that are monomeric, this involves a preliminary solution-phase assembly process into a growth unit having some symmetry prior to addition to the lattice, recapitulating the initial stages of the nucleation process. If this model is correct then fluids and crystal growth models assuming a strictly monodisperse nutrient solution need to be revised. This model has been developed from experimental evidence based upon face growth rate, AFM, and fluorescence energy transfer data for the nucleation and growth of tetragonal lysozyme crystals.

Pusey, Marc L.↗

Fluid Dynamics of Bubbly Liquids

Experiments have been performed to study the average flow properties of inertially dominated bubbly liquids which may be described by a novel analysis. Bubbles with high Reynolds number and low Weber number may produce a fluid velocity disturbance that can be approximated by a potential flow. We studied the behavior of suspensions of bubbles of about 1.5 mm diameter in vertical and inclined channels. The suspension was produced using a bank of 900 glass capillaries with inner diameter of about 100 microns in a quasi-steady fashion. In addition, salt was added to the suspension to prevent bubble-bubble coalescence. As a result, a nearly monodisperse suspension of bubble was produced. By increasing the inclination angle, we were able to explore an increasing amount of shear to buoyancy motion. A pipe flow experiment with the liquid being recirculated is under construction. This will provide an even larger range of shear to buoyancy motion. We are planning a microgravity experiment in which a bubble suspension is subjected to shearing in a couette cell in the absence of a buoyancy-driven relative motion of the two phases. By employing a single-wire, hot film anemometer, we were able to obtain the liquid velocity fluctuations. The shear stress at the wall was measured using a hot film probe flush mounted on the wall. The gas volume fraction, bubble velocity, and bubble velocity fluctuations were measured using a homemade, dual impedance probe. In addition, we also employed a high-speed camera to obtain the bubble size distribution and bubble shape in a dilute suspension. A rapid decrease in bubble velocity for a dilute bubble suspension is attributed to the effects of bubble-wall collisions. The more gradual decrease of bubble velocity as gas volume fraction increases, due to subsequent hindering of bubble motion, is in qualitative agreement with the predictions of Spelt and Sangani for the effects of potential-flow bubble-bubble interactions on the mean velocity. The ratio of the bubble velocity variance to the square of the mean is 0(0.1). For these conditions Spelt and Sangani predicted that the homogeneous suspension would be unstable and clustering into horizontal rafts will take place. Evidence for bubble clustering is obtained by analysis of video images. The liquid velocity variance is larger than would be expected for a homogeneous suspension and the liquid velocity frequency spectrum indicates the presence of velocity fluctuations that are slow compared with the time for the passage of an individual bubble. These observations provide further evidence for bubble clustering.

Tsang, Y. H.↗

Measurements of Turbulence Attenuation by a Dilute Dispersion of Solid Particles in Homogeneous Isotropic Turbulence

This research addresses turbulent gas flows laden with fine solid particles at sufficiently large mass loading that strong two-way coupling occurs. By two-way coupling we mean that the particle motion is governed largely by the flow, while the particles affect the gas-phase mean flow and the turbulence properties. Our main interest is in understanding how the particles affect the turbulence. Computational techniques have been developed which can accurately predict flows carrying particles that are much smaller than the smallest scales of turbulence. Also, advanced computational techniques and burgeoning computer resources make it feasible to fully resolve very large particles moving through turbulent flows. However, flows with particle diameters of the same order as the Kolmogorov scale of the turbulence are notoriously difficult to predict. Some simple flows show strong turbulence attenuation with reductions in the turbulent kinetic energy by up to a factor of five. On the other hand, some seemingly similar flows show almost no modification. No model has been proposed that allows prediction of when the strong attenuation will occur. Unfortunately, many technological and natural two-phase flows fall into this regime, so there is a strong need for new physical understanding and modeling capability. Our objective is to study the simplest possible turbulent particle-laden flow, namely homogeneous, isotropic turbulence with a uniform dispersion of monodisperse particles. We chose such a simple flow for two reasons. First, the simplicity allows us to probe the interaction in more detail and offers analytical simplicity in interpreting the results. Secondly, this flow can be addressed by numerical simulation, and many research groups are already working on calculating the flow. Our detailed data can help guide some of these efforts. By using microgravity, we can further simplify the flow to the case of no mean velocity for either the turbulence or the particles. In fact the addition of gravity as a variable parameter may help us to better understand the physics of turbulence attenuation. The experiments are conducted in a turbulence chamber capable of producing stationary or decaying isotropic turbulence with nearly zero mean flow and Taylor microscale Reynolds numbers up to nearly 500. The chamber is a 410 mm cubic box with the corners cut off to make it approximately spherical. Synthetic jet turbulence generators are mounted in each of the eight corners of the box. Each generator consists of a loudspeaker forcing a plenum and producing a pulsed jet through a 20 mm diameter orifice. These synthetic jets are directed into ejector tubes pointing towards the chamber center. The ejector tubes increase the jet mass flow and decrease the velocity. The jets then pass through a turbulence grid. Each of the eight loudspeakers is forced with a random phase and frequency. The resulting turbulence is highly Isotropic and matches typical behavior of grid turbulence. Measurements of both phases are acquired using particle image velocimetry (PIV). The gas is seeded with approximately 1 micron diameter seeding particles while the solid phase is typically 150 micron diameter spherical glass particles. A double-pulsed YAG laser and a Kodak ES-1.0 10-bit PIV camera provide the PIV images. Custom software is used to separate the images into individual images containing either gas-phase tracers or large particles. Modern high-resolution PIV algorithms are then used to calculate the velocity field. A large set of image pairs are acquired for each case, then the results are averaged both spatially and over the ensemble of acquired images. The entire apparatus is mounted in two racks which are carried aboard NASA's KC-135 Flying Microgravity Laboratory. The rack containing the turbulence chamber, the laser head, and the camera floats freely in the airplane cabin (constrained by competent NASA personnel) to minimize g-jitter.

Eaton, John↗