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At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS2004

Solution-Phase Processes of Macromolecular Crystallization

We have proposed, for the tetragonal form of chicken egg lysozyme, that solution phase assembly processes are needed to form the growth units for crystal nucleation and growth. The starting point for the self-association process is the monomeric protein, and the final crystallographic symmetry is defined by the initial dimerization interactions of the monomers and subsequent n-mers formed, which in turn are a function of the crystallization conditions. It has been suggested that multimeric proteins generally incorporate the underlying multimers symmetry into the final crystallographic symmetry. We posed the question of what happens to a protein that is known to grow as an n-mer when it is placed in solution conditions where it is monomeric. The trypsin-treated, or cut, form of the protein canavalin (CCAN) has been shown to nucleate and grow crystals as a trimer from neutral to slightly acidic solutions. Under these conditions the solution is composed almost wholly of trimers. The insoluble protein can be readily dissolved by weakly basic solution, which results in a solution that is monomeric. There are three possible outcomes to an attempt at crystallization of the protein under monomeric (high pH) conditions: 1) we will obtain the same crystals as under trimer conditions, but at different protein concentrations governed by the self association equilibria; 2) we will obtain crystals having a different symmetry, based upon a monomeric growth unit; 3) we will not obtain crystals. Obtaining the first result would be indicative that the solution-phase self-association process is critical to the crystal nucleation and growth process. The second result would be less clear, as it may also reflect a pH-dependent shift in the trimer-trimer molecular interactions. The third result, particularly for experiments in the transition pH's between trimeric and monomeric CCAN, would indicate that the monomer does not crystallize, and that solution phase self association is not part of the crystal nucleation and growth path. Results are presented for crystallization experiments of CCAN over the pH 6.8 to 9.6 range.

Pusey, Marc L.↗
NASA NTRS2002

Tetragonal Lysozyme Nucleation and Crystal Growth: The Role of the Solution Phase

Experimental evidence indicates a dominant role of solution phase interactions in nucleating and growing tetragonal lysozyme crystals. These interactions are extensive, even at saturation, and may be a primary cause of misoriented regions in crystals grown on Earth. Microgravity, by limiting interfacial concentrations to diffusion-controlled levels, may benefit crystal quality by also reducing the extent of associated species present at the interface.

Pusey, Marc L.↗
NASA NTRS1989

Polymer solution phase separation: Microgravity simulation

In many multicomponent systems, a transition from a single phase of uniform composition to a multiphase state with separated regions of different composition can be induced by changes in temperature and shear. The density difference between the phase and thermal and/or shear gradients within the system results in buoyancy driven convection. These differences affect kinetics of the phase separation if the system has a sufficiently low viscosity. This investigation presents more preliminary developments of a theoretical model in order to describe effects of the buoyancy driven convection in phase separation kinetics. Polymer solutions were employed as model systems because of the ease with which density differences can be systematically varied and because of the importance of phase separation in the processing and properties of polymeric materials. The results indicate that the kinetics of the phase separation can be performed viscometrically using laser light scattering as a principle means of following the process quantitatively. Isopycnic polymer solutions were used to determine the viscosity and density difference limits for polymer phase separation.

Cerny, Lawrence C.↗
NASA NTRS2002

Tetragonal Lysozyme Nucleation and Crystal Growth: The Role of the Solution Phase

Lysozyme, and most particularly the tetragonal form of the protein, has become the default standard protein for use in macromolecule crystal nucleation and growth studies. There is a substantial body of experimental evidence, from this and other laboratories, that strongly suggests this proteins crystal nucleation and growth is by addition of associated species that are preformed by standard reversible concentration-driven self association processes in the bulk solution. The evidence includes high resolution AFM studies of the surface packing and of growth unit size at incorporation, fluorescence resonance energy transfer measurements of intermolecular distances in dilute solution, dialysis kinetics, and modeling of the growth rate data. We have developed a selfassociation model for the proteins crystal nucleation and growth. The model accounts for the obtained crystal symmetry, explains the observed surface structures, and shows the importance of the symmetry obtained by self-association in solution to the process as a whole. Further, it indicates that nucleation and crystal growth are not distinct mechanistically, but identical, with the primary difference being the probability that the particle will continue to grow or dissolve. This model also offers a possible mechanism for fluid flow effects on the growth process and how microgravity may affect it. While a single lysozyme molecule is relatively small (M.W. = 14,400), a structured octamer in the 4(sub 3) helix configuration (the proposed average sized growth unit) would have a M.W. = 115,000 and dimensions of 5.6 x 5.6 x 7.6 nm. Direct AFM measurements of growth unit incorporation indicate that units as wide as 11.2 nm and as long as 11.4 nm commonly attach to the crystal. These measurements were made at approximately saturation conditions, and they reflect the sizes of species that both added or desorbed from the crystal surface. The larger and less isotropic the associated species the more likely that it will be oriented to some degree in a flowing boundary layer, even at the low flow velocities measured about macromolecule crystals. Flow-driven effects resulting in misorientation upon addition to and incorporation into the crystal need only be a small fraction of a percentage to significantly affect the resulting crystal. One Earth, concentration gradient driven flow will maintain a high interfacial concentration, i.e., a high level (essentially that of the bulk solution) of solute association at the interface and higher growth rate. Higher growth rates mean an increased probability that misaligned growth units are trapped by subsequent growth layers before they can be desorbed and try again, or that the desorbing species will be smaller than the adsorbing species. In microgravity the extended diffusive boundary layer will lower the interfacial concentration. This results in a net dissociation of aggregated species that diffuse in from the bulk solution, i.e., smaller associated species, which are more likely able to make multiple attempts to correctly bind, yielding higher quality crystals.

Pusey, Marc L.↗
NASA NTRS1991

Cell separations and the demixing of aqueous two phase polymer solutions in microgravity

Partition in phase separated aqueous polymer solutions is a cell separation procedure thought to be adversely influenced by gravity. In preparation for performing cell partitioning experiments in space, and to provide general information concerning the demixing of immiscible liquids in low gravity, a series of phase separated aqueous polymer solutions have been flown on two shuttle flights. Fluorocarbon oil and water emulsions were also flown on the second flight. The aqueous polymer emulsions, which in one g demix largely by sedimentation and convection due to the density differences between the phases, demixed more slowly than on the ground and the final disposition of the phases was determined by the wetting of the container wall by the phases. The demixing behavior and kinetics were influenced by the phase volume ratio, physical properties of the systems and chamber wall interaction. The average domain size increased linearly with time as the systems demixed.

Brooks, Donald E.↗
NASA NTRS1987

Highly Non-Linear Optical (NLO) organic crystals

This research project involves the synthesis and characterization of organic materials having powerful nonlinear optical (NLO) properties and the growth of highly ordered crystals and monomolecular films of these materials. Research in four areas is discussed: theoretical design of new materials, characterization of NLO materials, synthesis of new materials and development of coupling procedures for forming layered films, and improvement of the techniques for vapor phase and solution phase growth of high quality organic crystals. Knowledge gained from these experiments will form the basis for experiments in the growth of these crystals.

Harris, J. Milton↗
NASA NTRS1988

Demixing kinetics of phase separated polymer solutions in microgravity

Phase separated solutions of two neutral polymers in buffer provide a useful and versatile medium for the partition separation of biological cells. However, the efficiency of such separations is orders of magnitude lower than the thermodynamic limit. To test the hypothesis that this inefficiency is at least partially due to the convection and sedimentation that occur during the gravity driven demixing that follows introduction of cells to the systems, a series of experiments were begun aimed at performing cell partition in a low g environment. Demixing of isopycnic three polymer solvent systems was studied, experiments were performed on KC-135 aircraft and one shuttle middeck experiment was completed. Analysis of the results of these experiments and comparisons with the predictions of scaling relations for the dependence of phase domain size on time, derived for a number of possible demixing mechanisms, are presented.

Brooks, D. E.↗
NASA NTRS2004

The Crystallization of Canavalin as a Function of pH and NaCl Concentration

We posed the question of what happens to a protein that is known to grow as an n-mer when it is placed in solution conditions where it is monomeric. The trypsin-treated, or cut, form of the protein canavalin (CCAN) has been shown to nucleate and grow crystals as a trimer from neutral to slightly acidic solutions. Under these conditions the solution is composed almost wholly of trimers. The crystalline protein can be readily dissolved by weakly basic solution, which has been proposed to result in a solution that is monomeric. There are three possible outcomes to an attempt at crystallization of the protein under monomeric (high pH) conditions: 1) we will obtain the same crystals as under trimer conditions, but at different protein concentrations governed by the self association equilibria; 2) we will obtain crystals having a different symmetry, based upon a monomeric growth unit; 3) we will not obtain crystals. Obtaining the first result would be indicative that the solution-phase self-association process is critical to the crystal nucleation and growth process. The second result would be less clear, as it may also reflect a pH-dependent shift in the trimer-trimer molecular interactions. The third result, particularly for experiments in the transition pH's between trimeric and monomeric CCAN, would indicate that the monomer does not crystallize, and that solution phase self association is not part of the crystal nucleation and growth path. Results are presented for crystallization experiments of CCAN over the pH 6.4 to 9.6 range. Fluorescence anisotropy, light scattering, and gel filtration experiments show that the solutions are primarily trimers, with association to form larger species occurring as a function of protein concentration.

Forsythe, Elizabeth L.↗
NASA NTRS2002

A Proposed Pathway for the Nucleation and Crystal Growth of the Tetragonal Form of Lysozyme

A number of factors, the shape and charge distribution anisotropy, multiple components in the solution (buffer + counter ion, precipitant, protein, and water), conformational flexibility, and large numbers of intermolecular contacts, all serve as complicating variables in understanding the nucleation and growth mechanism for macromolecules. Intermolecular contacts include hydrogen bonds, van der Waals, hydrophobic, salt bridges, and ion-mediated contacts. The latter interactions are stronger and give specificity while the others are weaker, more prevalent, and more promiscuous, i.e., can lead to a range of possible molecular interactions. We propose that for tetragonal lysozyme, and by extension many other monomeric proteins, there is a solution-phase assembly process to form 4(sub 3) helix structures that are the basic unit for nucleation. The formation of these structures is continuous and concentration dependent. They subsequently also servc as growth units, with that process then being a recapitulation of the nucleation process. The advantages of solution phase assembly are the immediate burying of the strongest interactions, removing them from subsequent participation in the nucleation and growth process, and the introduction of symmetry into the system, which also assists in the assembly process.

Pusey, Marc L.↗
NASA NTRS1986

Undercooled and rapidly quenched Ni-Mo alloys

Hypoeutectic, eutectic, and hypereutectic nickel-molybdenum alloys were rapidly solidified by both bulk undercooling and melt spinning techniques. Alloys were undercooled in both electromagnetic levitation and differential thermal analysis equipment. The rate of recalescence depended upon the degree of initial undercooling and the nature (faceted or nonfaceted) of the primary nucleating phase. Alloy melts were observed to undercool more in the presence of primary Beta (NiMo intermetallic) phase than in gamma (fcc solid solution) phase. Melt spinning resulted in an extension of molybdenum solid solubility in gamma nickel, from 28 to 37.5 at % Mo. Although the microstructures observed by undercooling and melt spinning were similar the microsegregation pattern across the gamma dendries was different. The range of microstructures evolved was analyzed in terms of the nature of the primary phase to nucleate, its subsequent dendritic growth, coarsening and fragmentation, and final solidification of interfenderitic liquid.

Tewari, S. N.↗
NASA NTRS1987

Undercooled and rapidly quenched Ni-Mo alloys

Hypoeutectic, eutectic, and hypereutectic nickel-molybdenum alloys were rapidly solidified by both bulk undercooling and melt spinning techniques. Alloys were undercooled in both electromagnetic levitation and differential thermal analysis equipment. The rate of recalescence depended upon the degree of initial undercooling and the nature (faceted or nonfaceted) of the primary nucleating phase. Alloy melts were observed to undercool more in the presence of primary Beta (NiMo intermetallic) phase than in gamma (fcc solid solution) phase. Melt spinning resulted in an extension of molybdenum solid solubility in gamma nickel, from 28 to 37.5 at. pct Mo. Although the microstructures observed by undercooling and melt spinning were similar, the microsegregation pattern across the gamma dendries was different. The range of microstructures evolved was analyzed in terms of the nature of the primary phase to nucleate, its subsequent dendritic growth, coarsening and fragmentation, and final solidification of interfenderitic liquid.

Tewari, S. N.↗
NASA NTRS1992

Phase-field model for isothermal phase transitions in binary alloys

A new phase field model is described which models isothermal phase transitions between ideal binary alloy solution phases. Equations are developed for the temporal and spatial variation of the phase field, which describes the identity of the phase, and of the composition. An asymptotic analysis, as the gradient energy coefficient of the phase field becomes small, was conducted. From the analysis, it is shown that the model recovers classical sharp interface models of this situation when the interfacial layers are thin, and they show how to relate the parameters appearing in the phase field model to material and growth parameters in real systems. Further, three stages of temporal evolution are identified: the first corresponding to interfacial genesis which occurs very rapidly; the second to interfacial motion controlled by the local energy difference across the interface and diffusion; the last taking place on a long time scale in which curvature effects are important and which correspond to Ostwald ripening. The results of the numerical calculations are presented.

Wheeler, A. A.↗