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At least 883 records · Page 49
All sourcesNASA NTRSDOE OSTI
NASA NTRS1994

Noble gases in presolar diamonds I: Three distinct components and their implications for diamond origins

High-purity separates of presolar diamond were prepared from 14 primitive chondrites from 7 compositional groups. Their noble gases were measured using stepped pyrolysis. Three distinct noble gas components are present in diamonds, HL, P3, and P6, each of which is found to consist of five noble gases. P3, released between 200 C and 900 C, has a 'planetary' elemental abundance pattern and roughly 'normal' isotopic ratios. HL, consisting of isotopically anomalous Xe-HL and Kr-H, Ar with high Ar-38/Ar-36, and most of the gas making up Ne-A2 and He-A, is released between 1100 C and 1600 C. HL has 'planetary' elemental ratios, except that it has much more He and Ne than other known 'planetary' components. HL gases are carried in the bulk diamonds, not in some trace phase. P6 has a slightly higher median release temperature than HL and is not cleanly separated from HL by stepped pyrolysis. Our data suggest that P6 has roughly 'normal' isotopic compositions and 'planetary' elemental ratios. Both P3 and P6 seem to be isotopically distinct from P1, the dominant 'planetary' noble-gas component in primitive chondrites. Release characteristics suggest that HL and P6 are sited in different carriers within the diamond fractions, while P3 may be sited near the surfaces of the diamonds. We find no evidence of separability of Xe-H and Xe-L or other isotopic variations in the HL component. However, because approximately 10(exp 10) diamonds are required to measure a Xe composition, a lack of isotopic variability does not constrain diamonds to come from a single source. In fact, the high abundance of diamonds in primitive chondrites and the presence of at least three distinct noble-gas components strongly suggest that diamonds originated in many sources. Relative abundances of noble-gas components in diamonds correlate with degree of thermal processing, indicating that all meteorites sampled essentially the same mixture of diamonds. That mixture was probably inherited from the Sun's parent molecular cloud.

Huss, Gary R.↗
NASA NTRS1993

Tectonic controls on rift basin morphology: Evolution of the northern Malawi (Nyasa) rift

Radiometric (K-Ar and Ar-40/Ar-39) age determinations of volcanic and volcaniclastic rocks, combined with structural, gravity, and seismic reflection data, are used to constrain the age of sedimentary strata contained within the seismically and volcanically active northern Malawi (Nyasa) rift and to characterize changes in basin and flank morphologies with time. Faulting and volcanism within the Tukuyu-Karonga basin began at approximately 8.6 Ma, when sediments were deposited in abroad, initially asymmetric lake basin bounded on its northeastern side by a border fault system with minor topographic relief. Extensions, primarily by a slip along the border fault, and subsequent regional isostatic compensation led to the development of a 5-km-deep basin bounded by broad uplifted flanks. Along the low-relief basin margin opposite border fault, younger stratigraphic sequences commonly onlap older wedge-shaped sequences, although their internal geometry is often progradational. Intrabasinal faulting, flankuplift, and basaltic and felsic volcanism from centers at the northern end of the basin became more important at about 2.5 Ma when cross-rift transfer faults developed to link the Tukuyu-Karonga basin to the Rukwa basin. Local uplift and volcanic construction at the northern end of the basin led to a southeastward shift in the basin's depocenter. Sequence boundaries are commonly erosional along this low-relief (hanging wall) margin and conformable in the deep lake basin. The geometry of stratigraphic sequences and the distribution of the erosion indicate that horizontal and vertical crustal movements both across and along the length of the rift basin led to changes in levels of the lake, irrespective of paleoclimatic fluctuations.

Ebinger, C. J.↗
NASA NTRS1994

Mars atmospheric loss and isotopic fractionation by solar-wind-induced sputtering and photochemical escape

We examine the effects of the loss of Mars atmospheric constituents by solar-wind-induced sputtering and by photochemical escape during the past 3.8 billion years. Sputtering is capable of efficiently removing species from the upper atmosphere, including the light noble gases; nitrogen and oxygen are removed by photochemical processes as well. Due to diffusive separation (by mass) above the homopause, removal from the top of the atmosphere will fractionate the isotopes of each species, with the lighter mass being preferentially lost. For carbon and oxygen, this allows us to determine the size of nonatmospheric reservoirs which mix with the atmosphere; these reservoirs can be CO2 adsorbed in the regolith and H2O in the polar ice caps. We have constructed both simple analytical models and time-dependent models of the loss of volatiles from and supply to the martian atmosphere. Both argon and neon require continued replenishment from outgassing over geologic time. For argon, sputtering loss explains the fractionation of (Ar-36)/(Ar-38) without requiring a distinct epoch of hydrodynamic escape (although fractionation of Xe isotopes still requires very early hydrodynamic loss). For neon, the current (Ne-22)/(Ne-20) ratio represents a balance between loss to space and continued resupply from the interior; the similarity of the ratio to the terrestrial value is coincidental. For nitrogen, the loss by both sputtering and photochemical escape would produce a fractionation of (N-15)/(N-14) larger than observed; an early, thicker carbon dioxide atmosphere could mitigate the nitrogen loss and produce the observed fractionation, as could continued outgassing of juvenile nitorgen. Based on the isotopic constraints, the total amount of carbon dioxide lost over geologic time is probably on the order of tens of millibars rather than a substantial fraction of a bar. The total loss from solar-wind-induced sputtering and photochemical escape, therefore, does not seem able to explain the loss of a putative thick, early atmosphere withput requiring formation of extensive surface carbonate deposits or other nonatmospheric reservoirs for CO2.

Jakosky, Bruce M.↗
NASA NTRS1995

Argon and neon in Galactic nebulae

KAO observations of the 6.98 micron line of (Ar II), and KAO and ground-based observations of the 8.99 micron line of (Ar III) and the 12.8 micron line of (Ne II) are presented for a number of Galactic H II regions and planetary nebulae.

Simpson, Janet P.↗
NASA NTRS1995

Space qualification of IR-reflecting coverslides for GaAs solar cells

Improvements to GaAs solar array performance, from the use on solar cell coverslides of several reflecting coatings that reject unusable portions of the solar spectrum, are quantified. Blue-red-rejection (BRR) coverslides provide both infrared reflection (IRR) and ultraviolet rejection (UVR). BRR coverslides were compared to conventional antireflection (AR) and ultraviolet (UV) coated coverslides. A 2% improvement in peak-power output, relative to that from Ar-coated coverslides, is seen for cells utilizing BRR coverslides with the widest bandpass. Coverslide BRR-filter bandpass width and covered-solar-cell short-circuit current is a function of incident light angle and the observed narrower-bandpass filters are more sensitive to change in angle from the normal than are wide-bandpass filters. The first long-term (3000 hours) UV testing of unirradiated and 1 MeV electron-irradiated GaAs solar cells, with multilayer-coated coverslides to reduce solar array operating temperature, has indicated that all multilayer coatings on coverslides and solar cells will experience degradation from the space environment (UV and/or electrons). Five types of coverslide coatings, designed for GaAs solar cells, were tested as part of a NASA-sponsored space-flight qualification for BRR, multi-layer-coated, coverslides. The reponse to the different radiations varied with the coatings. The extent of degradation and its consequences on the solar cell electrical characteristics depend upon the coatings and the radiation. In some cases, an improved optical coupling was observed during long-term UV exposure to the optical stack. The benefits of multi-layered solar cell optics may depend upon both the duration and the radiation environment of a mission.

Meulenberg, Andrew↗
NASA NTRS1996

A study of GPS measurement errors due to noise and multipath interference for CGADS

This report describes a study performed by the Colorado Center for Astrodynamics Research (CCAR) on GPS measurement errors in the Codeless GPS Attitude Determination System (CGADS) due to noise and multipath interference. Preliminary simulation models fo the CGADS receiver and orbital multipath are described. The standard FFT algorithms for processing the codeless data is described and two alternative algorithms - an auto-regressive/least squares (AR-LS) method, and a combined adaptive notch filter/least squares (ANF-ALS) method, are also presented. Effects of system noise, quantization, baseband frequency selection, and Doppler rates on the accuracy of phase estimates with each of the processing methods are shown. Typical electrical phase errors for the AR-LS method are 0.2 degrees, compared to 0.3 and 0.5 degrees for the FFT and ANF-ALS algorithms, respectively. Doppler rate was found to have the largest effect on the performance.

Axelrad, Penina↗
NASA NTRS1996

The modelling of symmetric airfoil vortex generators

An experimental study is conducted to determine the dependence of vortex generator geometry and impinging flow conditions on shed vortex circulation and crossplane peak vorticity for one type of vortex generator. The vortex generator is a symmetric airfoil having a NACA 0012 cross-sectional profile. The geometry and flow parameters varied include angle-of-attack alfa, chordlength c, span h, and Mach number M. The vortex generators are mounted either in isolation or in a symmetric counter-rotating array configuration on the inside surface of a straight pipe. The turbulent boundary layer thickness to pipe radius ratio is delta/R = 0. 17. Circulation and peak vorticity data are derived from crossplane velocity measurements conducted at or about 1 chord downstream of the vortex generator trailing edge. Shed vortex circulation is observed to be proportional to M, alfa, and h/delta. With these parameters held constant, circulation is observed to fall off in monotonic fashion with increasing airfoil aspect ratio AR. Shed vortex peak vorticity is also observed to be proportional to M, alfa, and h/delta. Unlike circulation, however, peak vorticity is observed to increase with increasing aspect ratio, reaching a peak value at AR approx. 2.0 before falling off.

Reichert, B. A.↗
NASA NTRS1994

X-ray Photoelectron Spectroscopy Study of Argon-Plasma-Treated Fluoropolymers

Films of poly(tetrafluoroethylene) (PTFE) and of a tetrafluoroethylene-perfluoroalkyl vinyl ether (approximately 49:1) copolymer (PFA) were exposed to a radio-frequency argon plasma and then examined by X-ray photoelectron spectroscopy (XPS). The use of fluoropolymer films nearly free of surface hydrocarbon contamination as well as the use of a monochromatized X-ray source for XPS removed two factors contributing to conflicting reports on the effect of exposure time on the fluorine-to-carbon (F/C) and oxygen-to-carbon (O/C) ratios for several Ar-plasma-treated fluoropolymers. Contrary to literature indications, a common pattern was found for PTFE and PFA: a moderate decrease in F/C ratio (from 1.99 to 1.40, and from 1.97 to 1.57, respectively), together with a moderate increase in O/C ratio (from negligible to about 0.10, and from 0.012 to about O.10, respectively) at very short exposures, after which the F/C ratios remained essentially constant on prolonged exposures, while the O/C ratios for PTFE and PFA leveled off at 0.11 and 0.15, respectively. The XPS C(sub 1s), spectra for these polymers exposed to the Ar plasma for 20 min were similar and presented, besides a prominent peak at 292.0 eV (CF2,) and a minor peak at 294.0 or 294.1 eV (CF3), a composite band of four curve-resolved peaks (approximately 285-290 eV) representing various CH, CC, CO, CN, and CF functionalities.

Golub, Morton A.↗
NASA NTRS1997

Application of Interface Technology in Nonlinear Analysis of a Stitched/RFI Composite Wing Stub Box

A recently developed interface technology was successfully employed in the geometrically nonlinear analysis of a full-scale stitched/RFI composite wing box loaded in bending. The technology allows mismatched finite element models to be joined in a variationally consistent manner and reduces the modeling complexity by eliminating transition meshing. In the analysis, local finite element models of nonlinearly deformed wide bays of the wing box are refined without the need for transition meshing to the surrounding coarse mesh. The COMET-AR finite element code, which has the interface technology capability, was used to perform the analyses. The COMET-AR analysis is compared to both a NASTRAN analysis and to experimental data. The interface technology solution is shown to be in good agreement with both. The viability of interface technology for coupled global/local analysis of large scale aircraft structures is demonstrated.

Wang, John T.↗
NASA NTRS1996

Argon-40/Argon-39 Age Spectra of Apollo 17 Highlands Breccia Samples by Laser Step Heating and the Age of the Serenitatis Basin

We have obtained high-resolution (21-63 steps) Ar-40/Ar-39 age spectra using a continuous laser system on 19 submilligram samples of melt rocks and clasts from Apollo 17 samples collected from the pre-Imbrian highlands in the easternmost part of the Serenitatis basin. The samples include poikilitic melt rocks inferred to have been formed in the Serenitatis basin-forming impact, aphanitic melt rock whose compositions vary and whose provenance is uncertain, and granulite, gabbro, and melt clasts. Three of the poikilitic melts have similar age spectrum plateau ages (72395,96, 3893 +/- 16 Ma (2sigma); 72535,7, 3887 +/- 16 Ma; 76315,150, 3900 +/- 16 Ma) with a weighted mean age of 3893 +/- 9 Ma, which we interpret as the best age for the Serenitatis basin- forming impact. Published Ar-40/Ar-39 age spectrum ages of Apollo 17 poikilitic melts are consistent with our new age but are much less precise. Two poikilitic melts did not give plateaus and the maxima in their age spectra indicate ages of greater than or equal to 3869 Ma (72558,7) and greater than or equal to 3743 Ma (77135,178). Plateau ages of two poikilitic melts and two gabbro clasts from 73155 range from 3854 +/- 16 Ma to 3937 +/- 16 Ma and have probably been affected by the ubiquitous (older?) clasts and by post- formation heating (impact) events. Plateau ages from two of the aphanitic melt 'blobs' and two granulites in sample 72255 fall in the narrow range of 3850 q 16 Ma to 3869 q 16 Ma with a weighted mean of 3862 +/- 8 Ma. Two of the aphanitic melt blobs from 72255 have ages of 3883 +/- 16 Ma and greater than or equal to 3894 Ma, whereas a poikilitic melt clast (of different composition from the 'Serenitatis' melts) has an age of 3835 +/- 16 Ma, which is the upper limit for the accretion of 72255. These data suggest that either the aphanitic melts vary in age, as is also suggested by their varying chemical compositions, or they formed in the 72255 accretionary event about 3.84-3.85 Ga and older relict material is responsible for the dispersion of ages. In any case the aphanitic melts do not appear to be Serenitatis products. Our age for the Serenitatis impact shows, on the basis of the isotopic age evidence alone, that Serenitatis is greater than 20-25 Ma and probably greatr than 55-60 Ma older than Imbrium (less than or equal to 3870 Ma and probably less than or equal to 3836 Ma (Dalrymple and Ryder, 19931). Noritic granulite sample 78527 has a plateau age of 4146 +/- 17 Ma, representing a minimum age for cooling of this sample in the early lunar crust. So far there is no convincing evidence in the lunar melt rock record for basin-forming impacts significantly older than 3.9 Ga.

Dalrymple, G. Brent↗
NASA NTRS1998

The Improvement of Ion Plated Ag and Au Film Adherence to Si3N4 and SiC Surfaces for Increased Tribological Performance

A modified dc-diode plating system, utilizing a metallic screen cage as a cathode and referred as SCREEN CAGE ION PLATING (SCIP), is used to deposit Ag and Au lubricating films on Si3N4 and SiC surfaces. When deposition is performed in Ar or N2, glow discharge, the surface displays poor adhesive strength (less than 5 MPa). A dramatic increase in adhesive strength (less than 80 MPa) is achieved when plating is performed in a reactive 50% 02 + 50% Ar glow discharge. The excited/ionized oxygen species (O2(+)/O(+) in the glow discharge contribute to the oxidation of the Si3N4 or SiC surfaces as determined by X-ray Photoelectron Spectroscopy (XTS) depth profiling. The reactively sputter-oxidized S3N4 or SiC surfaces and the activated-oxidized-metastable Ag or Au species formed in the plasma cooperatively contribute to the increased adherence. As a result, the linear thermal expansion coefficient mismatch at the interface is reduced. These lubricating Ag and Au films under sliding conditions reduce the friction coefficient by a factor of 2-1/2 to 4.

Spalvins, Talivaldis↗
NASA NTRS1998

Cross Sections for Electron Impact Excitation of Ions Relevant to Planetary Atmospheres Observation

The goal of this research grant was to calculate accurate oscillator strengths and electron collisional excitation strengths for inelastic transitions in atomic species of relevance to Planetary Atmospheres. Large scale configuration-interaction atomic structure calculations have been performed to obtain oscillator strengths and transition probabilities for transitions among the fine-structure levels and R-matrix method has been used in the calculations of electron-ion collision cross sections of C II, S I, S II, S III, and Ar II. A number of strong features due to ions of sulfur have been detected in the spectra of Jupiter satellite Io. The electron excitation cross sections for the C II and S II transitions are studied in collaboration with the experimental atomic physics group at the Jet Propulsion Laboratory. There is excellent agreement between experiment and theory which provide an accurate and broad-base test of the ability of theoretical methods used in the calculation of atomic processes. Specifically, research problems have been investigated for: electron impact excitation cross sections of C II: electron impact excitation cross sections of S III; energy levels and oscillator strengths for transitions in S III; collision strengths for electron collisional excitation of S II; electron impact excitation of inelastic transitions in Ar II; oscillator strengths of fine-structure transitions in neutral sulfur; cross sections for inelastic scattering of electrons from atomic nitrogen; and excitation of atomic ions by electron impact.

Tayal, Swaraj S.↗
NASA NTRS1998

The Mid-Infrared Spectrum of the Galactic Center: A Starburst Nucleus

Using the Michelson interferometer on the Midcourse Space Experiment (MSX), we have taken spectra of many positions in the central 25 min of the Galactic Center (GC) with a 6 min x 9 min FOV. The spectral coverage was 380 to 1700/ cm (6 to 26 microns) and the resolution was approx. 21/cm. The spectra exhibit strong UIR/PAH features at 6.2, 7.7, 8.6 and 11.3 microns, in addition to the ionic lines of (Ne II), at 12.8 microns, (S III) 18.7 microns, and (Ar II) 6.98 microns. There are deep silicate absorption features at 10 and 18 microns and a cold continuum increasing at the longest wavelengths. Additional weak features are present in the spectra. We discuss the variation in the extinction at 10 microns as a function of location in the GC. Compared to the MSX spectrum of the Orion nebula, smoothed to the same resolution and multiplied by the estimated GC extinction, the GC spectra have similar PAH features, but the Orion Nebula also has strong lines of (He III) 15.6 microns, (S IV) 10.5 microns, and (Ar III) 8.99 microns and its 25 microns continuum is stronger (colder). Thus, the GC exhibits the mid-IR spectrum of a low excitation H II region and a nearby molecular cloud with a surface photodissociation region (PDR). This is in excellent agreement with the canonical model of a starburst nucleus in which the hot stars and molecular clouds are randomly distributed. The outer surfaces of the clouds are photodissociated and ionized by the photons from the stars located outside the clouds. The PAH molecules are transiently heated by the stellar photons. Since the exciting stars are located well outside the clouds, the radiation field is dilute compared to a newly-formed blister H II region like Orion; this dilute radiation field causes the relatively low excitation of the ionic lines.

Simpson, J. P.↗
NASA NTRS1998

Midcourse Space Experiment Spectra of the Orion Nebula and the Implications for Abundances in the Interstellar Medium

Spectra of the Orion Nebula were obtained with the Midcourse Space Experiment Spirit 3 interferometer from 370 to 2000 cm(exp -1) with 2 cm(exp -1) resolution in a 6' x 9' field of view (FOV) in 1996 November. Lines were detected of [S III] 534.4 cm(exp -1), [Ne III] 642.9 cm(exp -1), [Ne II] 780.4 cm(exp -1), [S IV] 951.4 cm(exp -1), [Ar III] 1112.2 cm(exp -1), [Ar II] 1431.6 cm(exp -1), H (7-6) 808.3 cm(exp -1), H (8-6) 1332.9 cm(exp -1), H (6-5) 1340.5 cm(exp -1), H2(S1) 587.0 cm(exp -1), H2(S2) 814.4 cm(exp -1), H2(S3) 1034.7 cm(exp -1), H2(S4) 1246.1 cm(exp -1), and H2(S5) 1447.3 cm(exp -1). The following abundances were determined from these lines: Ne/H = 9.9 +/- 1.1 x 10(exp -5), S/H = 8.1 +/- 1.1 x 10(exp -6), and Ar/H = 2.5 +/- 0.2 x 10(exp -6). These abundances are all less than solar and confirm that the Sun is overabundant in heavy elements without the need for correction for the composition of interstellar dust. The low sulfur abundance compared with solar is an indication that a significant amount of the sulfur in Orion is in dust grains. The FOV-averaged molecular hydrogen column density is approximately 1.6 x 10(exp 20) cm(exp -2) for an excitation temperature of approximately 670 K and an extinction correction corresponding to an optical depth of 1.5 at 9.7 micrometers. The unidentified infrared emission features at 6.2, 7.7, 8.6, 11.3, and 12.7 micrometers, attributable to polycyclic aromatic hydrocarbons, were also detected. A prominent, broad silicate feature centered near 18 micrometer and additional weak features were detected and are discussed.

Simpson, J. P.↗
NASA NTRS1999

Constructing the Coronal Magnetic Field by Correlating Parameterized Magnetic Field Lines with Observed Coronal Plasma Structures

A method is presented for constructing the coronal magnetic field from photospheric magnetograms and observed coronal loops. A set of magnetic field lines generated from magnetogram data is parameterized and then deformed by varying the parameterized values. The coronal flux tubes associated with this field are adjusted until the correlation between the field lines and the observed coronal loops is maximized. A mathematical formulation is described which ensures that (1) the normal component of the photospheric field remains unchanged, (2) the field is given in the entire corona over an active region, (3) the field remains divergence-free, and 4electric currents are introduced into the field. It is demonstrated that a parameterization of a potential field, comprising a radial stretching of the field, can provide a match for a simple bipolar active region, AR 7999, which crossed the central meridian on 1996 November 26. The result is a non-force-free magnetic field with the Lorentz force being of the order of 10(exp -5.5) g per s(exp 2) resulting from an electric current density of 0.79 micro A per m(exp 2). Calculations show that the plasma beta becomes larger than unity at a strong non-radial currents requires low height of about 0.25 solar radii supporting the non-force-free conclusion. The presence of such strong non-radial currents requires large transverse pressure gradients fo maintain a magnetostatic atmosphere, required by the relatively persistent nature of the coronal structures observed in AR 7999. This scheme is an important tool in generating a magnetic field solution consistent with the coronal flux tube observations and the observed photospheric magnetic field.

Allen, Gary G.↗
NASA NTRS1999

Coronal Dimmings and Energetic CMEs

We have analyzed the coronal dimmings for seven fast (> 600 km/s) coronal mass ejections (CMEs) occurring between 23 April and 9 May which were associated with flares from NOAA active region (AR) 8210. These dimming regions were identified by their strong depletion in coronal emission within a half hour of the estimated time of CME lift-off. They included areas which were as dark as quiescent coronal holes as well as other regions with weaker brightness depletions. We found that the extended dimming areas in these events generally mapped out the apparent "footprint" of the CME. In two of the seven cases, a pair of dimmings were more or less symmetrically positioned north and south of the flare site. In the five remaining cases, the dimmings were most prominent to the north of AR 8210 (approximately S15 latitude) and extended well north of the solar equator, consistent with the locations of the CMEs. We discuss the implications of these results for the sigmoid/double dimming/flux rope model of CMEs.

Thompson, B. J.↗
NASA NTRS1994

Status of Diffused Junction p(+)n InP Solar Cells for Space Applications

Recently, we have succeeded in fabricating diffused junction p(+)n(Cd,S) InP solar cells with measured AMO, 25 C open circuit voltage (V(sub OC)) of 887.6 mV, which, to the best of our knowledge, is higher than previously reported V(sub OC) values for any InP homojunction solar cells. The experiment-based projected achievable efficiency of these cells using LEC grown substrates is 21.3%. The maximum AMO, 25 C efficiency recorded to date on bare cells is, however, only 13.2%. This is because of large external and internal losses due to non-optimized front grid design, antireflection (AR) coating and emitter thickness. This paper summarizes recent advances in the technology of fabrication of p(+)n InP diffused structures and solar cells, resulted from a study undertaken in an effort to increase the cell efficiency. The topics discussed in this paper include advances in: 1) the formation of thin p(+) InP:Cd emitter layers, 2) electroplated front contacts, 3) surface passivation and 4) the design of a new native oxide/AI203/MgF2 three layer AR coating using a chemically-grown P-rich passivating oxide as a first layer. Based on the high radiation resistance and the excellent post-irradiation annealing and recovery demonstrated in the early tests done to date, as well as the projected high efficiency and low-cost high-volume fabricability, these cells show a very good potential for space photovoltaic applications.

Faur, Mircea↗
NASA NTRS2000

Preparation and Characterization of Fluorescent Derivatives of Chicken Egg White Lysozyme

Fluorescence is one of the most versatile and powerful tools for the study of macromolecules. While most proteins are intrinsically fluorescent, working at crystallization concentrations require the use of covalently prepared derivatives added as tracers. This approach requires derivatives that do not markedly affect the crystal packing. We have prepared a number of fluorescent derivatives of chicken egg white lysozyme with probes bound to one of two different sites on the protein molecule. Lucifer yellow, cascade blue, and 5-(2-aminoethyl)aminonapthalene-l-sulfonic acid (EDANS) have been attached to the side chain carboxyl of asp101 using a carbodiimide coupling procedure. asp101 lies within the active site cleft, and it is believed that the probes are at least partially "buried" within that cleft. Lucifer yellow and MANS probes with iodoacetamide reactive groups have been bound to hisl5, located on the "back side" of the molecule relative to the active site. The fluorescently labeled protein is readily purified from the starting material by cation exchange chromatography. All the derivatives fluoresce in both the solution and the crystalline states. Fluorescence characterization has focused on determining the bound probe quantum yields, lifetimes, absorption and emission spectra, and quenching by added solutes in comparison to the free probe. No appreciable changes are found in the lifetimes of any of the probes except for cascade blue, where Tau(sub free) = 3.52 ns vrs Tau(sub bound) = 2.8 ns. Spectral shifts are found in most cases. Particularly strong quenching upon binding is found in the case of the cascade blue derivative, likely due to probe interactions with the active site cleft. While none of the asp101 bound probes are well quenched by commonly employed solutes, such as potassium and sodium iodide, acrylamide, primuline, the chloride salts of manganese, cesium, and cobalt, trifluoroacetamide, trichloroethanol, and thallium iodide, in those cases where quenching is observed the bound probe is less efficiently quenched relative to the free probe. This indicates that the bound probes are less accessible to the bulk solution, an expected finding for attachment within the active site cleft. Attempts have been made to bind other molecules to these sites, with varying success. Interestingly, all three probes contain one or more sulfonate ((Ar-S03)-) groups. We have not been successful in binding analogous probes without sulfate groups such as pyrene, or with derivatized sulfonate groups such as dansyl type probes, analogous to MANS but where the sulfonate group is derivatized, Ar-S02-N2C2H7. None of the probes is rigidly bound to the protein, i.e., they all have a probe motion superimposed on that of the protein.

Sumida, John↗