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At least 19 records

Nucleation and Crystallization of Globular Proteins: What we Know and What is Missing

Recently. much progress has been made in understanding the nucleation and crystallization of globular proteins, including the formation of compositional and structural crystal defects, Insight into the interactions of (screened) protein macro-ions in solution, obtained from light scattering, small angle X-ray scattering and osmotic pressure studies. can guide the search for crystallization conditions. These studies show that the nucleation of globular proteins is governed by the same principles as that of small molecules. However, failure to account for direct and indirect (hydrodynamic) protein interactions in the solutions results in unrealistic aggregation scenarios. Microscopic studies of numerous proteins reveal that crystals grow by the attachment of growth units through the same layer-spreading mechanisms as inorganic crystals. Investigations of the growth kinetics of hen-egg-white lysozyme (HEWL) reveal non-steady behavior under steady external conditions. Long-term variations in growth rates are due to changes in step-originating dislocation groups. Fluctuations on a shorter timescale reflect the non-linear dynamics of layer growth that results from the interplay between interfacial kinetics and bulk transport. Systematic gel electrophoretic analyses suggest that most HEWL crystallization studies have been performed with material containing other proteins at percent levels. Yet, sub-percent levels of protein impurities impede growth step propagation and play a role in the formation of structural/compositional inhomogeneities. In crystal growth from highly purified HEWL solutions, however, such inhomogeneities are much weaker and form only in response to unusually large changes in growth conditions. Equally important for connecting growth conditions to crystal perfection and diffraction resolution are recent advances in structural characterization through high-resolution Bragg reflection profiling and X-ray topography.

Rosenberger, F.↗

Development of improved amorphous materials for laser systems

Crystallization calculations were performed in order to determine the possibility of forming a particular type of laser glass with the avoidance of devitrification in an outer space laboratory. It was demonstrated that under the homogenuous nucleating conditions obtainable in a zero gravity laboratory this laser glass may be easily quenched to a virtually crystal-free product. Experimental evidence is provided that use of this material as a host in a neodymium glass laser would result in more than a 10 percent increase in efficiency when compared to laser glass rods of a similar composition currently commercially available. Differential thermal analysis, thermal gradient oven, X-ray diffraction, and liquidus determination experiments were carried out to determine the basics of the crystallization behavior of the glass, and small-angle X-ray scattering and splat-cooling experiments were performed in order to provide additional evidence for the feasibility of producing this laser glass material, crystal free, in an outer space environment.

Neilson, G. F.↗

Morphology and Dynamic Mechanical Properties of Diglycidyl Ether of Bisphenol-A Toughened with Carboxyl-Terminated Butadiene-Acrylonitrile

The fracture toughness of an incorporation of a carboxyl-terminated butadiene acrylonitrile (CTBN) elastomer in diglycidyl ether bisphenol A (DGEBA) resin was investigated. Measurements of dynamic mechanical properties, scanning electron microscopy and small-angle X-ray scattering were carried out to characterize the state of cure, morphology and particle size and size distribution of the neat resins and their graphite fiber reinforced composites.

Hong, S. D.↗

Homogeneous versus heterogeneous crystal nucleation in Li2O-2SiO2 glass

When analyzing crystal nucleation in glasses, it is difficult to distinguish between homogeneous and heterogeneous nucleation. A method is proposed to investigate the nature of crystal nucleation in Li2O-2SiO2, and calculations are performed to determine under which conditions saturation effects help ascertain the nature of the nucleation. The capability of detecting impurity particles in unheated glass via standard micrographic techniques (SEM or REM) and small angle X-ray scattering (SAXS) is explored. Results indicate that if the maximum impurity particle densities do not exceed 2 x 10 to the 7th per cu cm then heterogeneous nucleation may be excluded and most impurity particles with densities in excess of 10 to the 10th per cu cm are detectable by SAXS. It is concluded that crystal nucleation in this system most probably occurs homogeneously.

Weinberg, M. C.↗

Effect of OH content on phase separation behavior of soda-silica glasses

The kinetics of phase separation in a gel and ordinary soda-silica glass are followed by use of small angle X-ray scattering. Also, the influence of OH on the phase separation behavior is studied. It is found that OH accelerates the growth of the secondary phase, and that gel and ordinary glasses of similar composition and OH concentration exhibit similar phase separation characteristics.

Neilson, G. F.↗

Physical aging in epoxy matrices and composites

Postcured specimens of Thornell 300 carbon-fiber/Fiberite 934 epoxy as well as Fiberite 934 epoxy resin were quenched from above the glass transition temperature and annealed at 140, 110, or 80 C for times up to 100,000 min. No weight gain or loss was observed during annealing at these temperatures, but significant time-dependent variations were observed in density, modulus, hardness, damping, moisture absorption ability, and thermal expansion characteristics. The relations between the excess thermodynamic properties of epoxy glasses and their time-dependent behavior are discussed. The discussion is illustrated by results obtained by differential scanning calorimetry, dynamic mechanical analysis, tensile testing, solid state nuclear magnetic resonance spectroscopy, and small-angle X-ray scattering.

Kong, Eric Siu-Wai↗

Effects of Melt Processing on Evolution of Structure in PEEK

We report on the effects of melt processing temperature on structure formation in Poly(ether-ether-ketone), PEEK. Real time Small Angle X-ray Scattering, SAXS, and thermal analysis are used to follow the melting behavior after various stages of processing. Assignment of peaks to structural entities within the material, the relative perfection of the crystals, and the possibility of their reorganization, are all influenced by the melt processing history. With the advent of high intensity synchrotron sources of X-radiation, polymer scientists gain a research tool which, when used along with thermal analysis, provides additional structural information about the crystals during growth and subsequent melting. PEEK is an engineering thermoplastic polymer with a very high glass transition temperature (145 C) and crystal melting point (337 C). PEEK has been the subject of recent studies by X-ray scattering in which melt and cold crystallization were followed in real-time. X-ray scattering and thermal studies have been used to address the formation of dual endothermic response which has been variously ascribed to lamellar insertion, dual crystal populations, or melting followed by re-crystallization. Another important issue is whether all of the amorphous phase is located in interlamellar regions, or alternatively whether some is located in "pockets" away from the crystalline lamellar stacks. The interpretation of scattering from lamellar stacks varies depending upon whether such amorphous pockets are formed. Some groups believe all of the amorphous phase is interlamellar. This leads to selection of a smaller thickness for the crystals. Other groups suggest that most amorphous phase is not interlamellar, and this leads to the suggestion that the crystal thickness is larger than the amorphous layer within the stacks. To investigate these ideas, we used SAXS and Differential Scanning Calorimetry to compare results of single and dual stage melt crystallization of PEEK using a treatment scheme involving annealing/crystallization at T(sub a1) followed by annealing at T(sub a2) where either T(sub a1) < T(sub a2) or T(sub a1) > T(sub a2). We proposed a model to explain multiple melting endotherms in PPS, treated according to one or two-stage melt or cold crystallization. Key features of this model are that multiple endotherms: (1) are due to reorganization/recrystallization after cold crystallization; and, (2) are dominated by crystal morphology after melt crystallization at high T. In other words, multiple distinct crystal populations are formed by the latter treatment, leading to observation of multiple melting. PEEK 45OG pellets (ICI Americas) were the starting material for this study. Films were compression molded at 400 C, then quenched to ice water. Samples were heated to 375 C in a Mettler FP80 hot stage and held for three min. to erase crystal seeds before cooling them to T(sub a1) = 280 C . Samples were held at T(sub a2) for a period of time, then immediately heated to 360 C. In the second treatment samples were held at T(sub a1) = 31 C for different crystallization times t(sub c) then cooled to 295 C and held 15 min. In situ (SAXS) experiments were performed at the Brookhaven National Synchrotron Light Source with the sample located inside the Mettler hot stage. The system was equipped with a two-dimensional position sensitive detector. The sample to detector distance was 172.7 cm and the X-ray wavelength was 1.54 Angstroms. SAXS data were taken continuously during the isothermal periods and during the heating to 360 C at 5 C/min. Each SAXS scan was collected for 30 sec. Since the samples were isotropic, circular integration was used to increase the signal to noise ratio. After dual stage melt crystallization with T(sub a1) < T(sub a2) the lower melting endotherm arises from holding at T(sub a1). During cooling a broad distribution of crystals forms, and the low-melting tail is perfected during T(sub al). Heating to T(sub a2) melts these imperfect crystals and allows others with greater average long spacing to form in their place. After dual stage crystallization with T(sub a1) > T(sub a2), the amount of space remaining for additional growth at T(sub a2) depends upon the holding time at T(sub a1). The long period of crystals formed at T(sub a2) is smaller than that formed at T(sub a1) due to growth in a now-restricted geometry. Perfection of crystals is seen as an increase of the intensity of the population scattering at higher s, while the intensity of the population scattering at lower s stays constant. During heating from below to above the minor endotherm, we see rapid decrease of the intensity of the X-ray scattering corresponding to the population of crystals scattering in the shoulder. Another important observation is that after the sample is annealed at 295 C, the shoulder intensity is restored once again. The population scattering at higher s remains longer before it disappears in the sample treated to the second stage of melt crystallization, compared to the sample crystallized with a single stage. This could be interpreted as an effect of continued perfection of the less perfect population, which is also reflected in the increased melting temperature of the smaller endotherm as the holding time at 295 C increases. In the corresponding DSC scans we see a shift in the area and the peak temperature of the lower melting endotherm with an increase of the annealing time.

Georgiev, Georgi↗

Interpretation of tails of X-ray bursts

Four reasons for ruling out the Alcock and Hatchett (1978) proposal concerning the tails of X-ray bursts are advanced. This proposal suggests that the tails of X-ray bursts observed during burst decay are due to the small-angle scattering of the original pulse of X-rays on interstellar dust grains; grains with a typical size of approximately 3 microns are assumed. The arguments against this theory involve differences in burst tail sizes sometimes observed for bursts from the same source; the different kinds of bursts emitted by MXB 1730-335 (rapid burster); an indication that MXB 1730-335 bursts have tails less than 2 s long; and the lack of correlation between relative strength of burst tails and the interstellar absorption.

Van Paradijs, J.↗

Reduction of the one-dimensional X-ray scattering data on mirror flats at NASA/Marshall Space Flight Center

Data on the scattering of X-rays from various mirror flats obtained from different vendors. The scattering data discussed in this section is obtained by a one dimensional proportional counter at X-ray energies of 8.06, 6.4 and 2.99 keV. X-rays are generated at one end of a 312.4m long tube which is under vacuum. This long tube provides a parallel beam of X-rays which is then collimated by a slit and allowed to scatter from a pair of mirror flats at small grazing angles of incidence. The slit and mirrors assembly is placed 182.4 meters from the other end of the tube where the proportional counter detector is located. The detector is sitting on an optical table which is pivoted so that it can rotate to intercept X-rays at a range of spatial locations. The optical table pivot is located 2.78 meters in front of the detector, and has an operational angular range of 350 arc minutes. Measured from the position of the mirror, this total angular range of the data is (350) (2.78/182.4) = 5.33 arcminutes.

Williams, A. C.↗

High energy, high resolution X-ray optics

The scientific goals of X-ray astronomy are considered to evaluate the relative advantages of using classical Wolter-1 optics or using a different approach. The portion of the X-ray band over 10 keV is unexploited in the present X-ray optics technology, and focussing in this portion of the band is crucial because nonfocussed experiments are background limited. The basic design of 'hard' X-ray optics is described theoretically emphasizing the very small angles of incidence in the grazing-incidence optics. Optimization of the signal-to-noise ratio is found to occur at a finite angular resolution. In real applications, the effective area reduced by the efficiency of the two reflections is 80 percent at energies up to 40 keV, and the quality of the reflecting surface can be monitored to minimize scattering. Focussing optics are found to offer improvements in signal-to-noise as well as more effective scientific return because microelectronic focal-plane technology is employed.

Weisskopf, Martin C.↗

Structure of the Circumnuclear Region of Seyfert 2 Galaxies Revealed by RXTE Hard X-Ray Observations of NGC 4945

NGC 4945 is one of the brightest Se.yfert galaxies on the sky at 100 keV, but is completely absorbed below 10 keV, implying an optical depth of the absorber to electron scattering of a few; its absorption column is probably the largest which still allows a direct view of the nucleus at hard X-ray energies. Our observations of it with the Rossi X-ray Timing Explorer (RXTE) satellite confirm the large absorption, which for a simple phenomenological fit using an absorber with Solar abundances implies a column of 4.5(sup 0.4, sub -0.4) x 10(exp 24) /sq cm. Using a a more realistic scenario (requiring Monte Carlo modeling of the scattering), we infer the optical depth to Thomson scattering of approximately 2.4. If such a scattering medium were to subtend a large solid angle from the nucleus, it should smear out any intrinsic hard X-ray variability on time scales shorter than the light travel time through it. The rapid (with a time scale of approximately a day) hard X-ray variability of NGC 4945 we observed with the RXTE implies that the bulk of the extreme absorption in this object does not originate in a parsec-size, geometrically thick molecular torus. Limits on the amount of scattered flux require that the optically thick material on parsec scales must be rather geometrically thin, subtending a half-angle < 10 deg. This is only marginally consistent with the recent determinations of the obscuring column in hard X-rays, where only a quarter of Seyfert 2s have columns which are optically thick, and presents a problem in accounting for the Cosmic X-ray Background primarily with AGN possessing the geometry as that inferred by us. The small solid angle of the obscuring material, together with the black hole mass (of approximately 1.4 x 10(exp 6) solar mass) from megamaser measurements. allows a robust determination of the source luminosity, which in turn implies that the source radiates at approximately 10% of the Eddington limit.

Madejski, G.↗

Collisional excitation of electron Landau levels in strong magnetic fields

The cross sections for the excitation and deexcitation of the quantized transverse energy levels of an electron in a magnetic field are calculated for electron-proton and electron-electron collisions in light of the importance of the cross sections for studies of X-ray pulsar emission. First-order matrix elements are calculated using the Dirac theory of the electron, thus taking into account relativistic effects, which are believed to be important in accreting neutron stars. Results for the collisional excitation of ground state electrons by protons are presented which demonstrate the importance of proton recoil and relativistic effects, and it is shown that electron-electron excitations may contribute 10 to 20% of the excitation rate from electron-proton scattering in a Maxwellian plasma. Finally, calculations of the cross section for electron-proton small-angle scattering are presented which lead to relaxation rates for the electron velocity distribution which are modified by the magnetic field, and to a possible increase in the value of the Coulomb logarithm.

Langer, S. H.↗

Thermal diffuse X-ray scattering in simple metals

Calculations are reported for the ionic structure factor and X-ray scattering cross section of sodium (at T=0 K and 90 K) and lithium (both isotopes at T=0 K) within the harmonic approximation. An evaluation of the appropriate displacement- displacement correlation function by the special point method circumvents the need for a multiphonon expansion. In the case of sodium, the structure in the one-phonon scattering was straightforwardly accounted for, and an approximate expansion was obtained for all multiphonon scattering. By treating core and conduction electrons on an equal footing, it is shown that information on the conduction electron system is present in the forward scattering component. In lithium the one-phonon cross section at small angles aids in the determination of the effective electron-ion interaction.

Straus, D. M.↗

The Response of the BATSE LADs to Radiation From the Crab Nebula and Plans for Radioactivity Studies on Space Station

The Burst And Transient Source Experiment (BATSE) onboard the Compton Gamma-Ray Observatory (CGRO) was designed to measure X-rays and gamma rays with energies from about 50 keV to above 2 MeV. As with many scientific investigations, the success of the original experiment lead to additional areas of research interest. In the case of BATSE the ability to observe the radiation from sources down to about 20 keV became readily apparent. This lead to a continuing program of measuring the spectrum of radiation from stellar objects at these lower energies. One of these, the Crab Nebula, has a very steady radiation flux and, thus, has become a "standard candle" for such measurements. The Large Area Detectors (LADS) on BATSE contain a 1.27-cm thick, 25.4-cm radius NaI(Tl) detector behind a 6.35-mm thick polystyrene Charged Particle Detector (CPD) used to "veto" charged particles signals. The detectors have been calibrated with a series of gamma and X-ray sources and the results carefully simulated with a Monte Carlo code. In the calibration process the computer simulation accounts for scattering from material in the counting room as well as the BATSE structure. For an orbiting detector, scattering from the entire spacecraft must be modeled as well as for all covering material over the detectors. Five years after CGRO was launched on April 5, 1991, a large body of observational data has been taken of the Crab Nebula. The technique used for these observations, and for many other X-ray sources, is Earth occultation. From the perspective of the spacecraft, the Earth occults most stellar objects once in orbit, i.e., the signal is lost as the source sets and is regained as the source rises. A careful analysis of the continuing signals from all sources measured allows for an accurate measurement of the spectrum of a given source. An analysis of this data from the Crab has indicated that the LADs are very responsive at energies as low as 20 keV-at energies below the range of calibration. While the model accounts for many of the interactions of the photons with the detectors, the observation of nonstatistical deviations at low energy and at small angles has suggested a need to recalibrate at energies where the attenuation effects are increasing exponentially.

Laird, C. E.↗

The Detection of Circumnuclear X-Ray Emission from the Seyfert Galaxy NGC 3516

We present the first high-resolution, X-ray image of the circumnuclear regions of the Seyfert 1 galaxy NGC 3516, using the Chandra X-ray Observatory (CXO). All three of the CXO observations reported were performed with one of the two grating assemblies in place, and here we restrict our analysis to undispersed photons (i.e. those detected in the zeroth-order). A previously-unknown X-ray source is detected approximately 6 arcsec (1.1h(sub 75)(exp -1) kpc) NNE of the nucleus (position angle approximately 29 degrees) which we designate CXOU 110648.1 + 723412. Its spectrum can be characterized as a power law with a photon index (Gamma) approximately 1.8 - 2.6, or as thermal emission with a temperature kT approximately 0.7 - 3 keV. Assuming a location within NGC 3516, isotropic emission implies a luminosity L approximately 2 - 8 x 10(exp 39)h(sub 75)(exp-2) erg s(exp -1) in the 0.4 - 2 keV band. If due to a single point source, the object is super-Eddington for a 1.4 solar mass neutron star. However, multiple sources or a small, extended source cannot be excluded using the current data. Large-scale extended S-ray emission is also detected out to approximately 10 arcsec (approximately 2h(sub 75)(exp -1) kpc) from the nucleus to the NE and SW, and is approximately aligned with the morphologies of the radio emission and extended narrow emission line region (ENLR). The mean luminosity of this emission is 1 - 5 x 10(exp 37)h(sub 75)(exp -2) erg s(exp -1) arcsec(exp -2), in the 0.4 - 2 keV band. Unfortunately the current data cannot usefully constrain its spectrum. These results are consistent with earlier suggestions of circumnuclear X-ray emissi in NGC 3516 based on ROSAT observations, and thus provide the first clear detection of extended X-ray emission in a Seyfert 1.0 galaxy. If the extended emission is due to scattering of the nuclear X-ray continuum, then the pressure in the X-ray emitting gas is at least two orders of magnitude too small to provide the confining medium for the ENLR clouds.

George, I. M.↗