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Bajt, Sasa

Publications and source records attributed to Bajt, Sasa.

Heterogeneity in M. tuberculosis β-lactamase inhibition by Sulbactam

Abstract For decades, researchers have elucidated essential enzymatic functions on the atomic length scale by tracing atomic positions in real-time. Our work builds on possibilities unleashed by mix-and-inject serial crystallography (MISC) at X-ray free electron laser facilities. In this approach, enzymatic reactions are triggered by mixing substrate or ligand solutions with enzyme microcrystals. Here, we report in atomic detail (between 2.2 and 2.7 Å resolution) by room-temperature, time-resolved crystallography with millisecond time-resolution (with timepoints between 3 ms and 700 ms) how the Mycobacterium tuberculosis enzyme BlaC is inhibited by sulbactam (SUB). Our results reveal ligand binding heterogeneity, ligand gating, cooperativity, induced fit, and conformational selection all from the same set of MISC data, detailing how SUB approaches the catalytic clefts and binds to the enzyme noncovalently before reacting to a trans- enamine. This was made possible in part by the application of singular value decomposition to the MISC data using a program that remains functional even if unit cell parameters change up to 3 Å during the reaction.

74 ATOMIC AND MOLECULAR PHYSICS↗

X-ray focusing with efficient high-NA multilayer Laue lenses

Multilayer Laue lenses are volume diffraction elements for the efficient focusing of X-rays. With a new manufacturing technique that we introduced, it is possible to fabricate lenses of sufficiently high numerical aperture (NA) to achieve focal spot sizes below 10 nm. The alternating layers of the materials that form the lens must span a broad range of thicknesses on the nanometer scale to achieve the necessary range of X-ray deflection angles required to achieve a high NA. This poses a challenge to both the accuracy of the deposition process and the control of the materials properties, which often vary with layer thickness. We introduced a new pair of materials—tungsten carbide and silicon carbide—to prepare layered structures with smooth and sharp interfaces and with no material phase transitions that hampered the manufacture of previous lenses. Using a pair of multilayer Laue lenses (MLLs) fabricated from this system, we achieved a two-dimensional focus of 8.4 × 6.8 nm 2 at a photon energy of 16.3 keV with high diffraction efficiency and demonstrated scanning-based imaging of samples with a resolution well below 10 nm. The high NA also allowed projection holographic imaging with strong phase contrast over a large range of magnifications. Furthermore, an error analysis indicates the possibility of achieving 1 nm focusing.

36 MATERIALS SCIENCE↗

Coordinated Microanalyses of Seven Particles of Probable Interstellar Origin from the Stardust Mission

Stardust, a NASA Discovery-class mission, was the first sample-return mission to return solid samples from beyond the Moon. Stardust was effectively two missions in one spacecraft: it returned the first materials from a known primitive solar system body, the Jupiter-family comet Wild 2; Stardust also returned a collector that was exposed to the contemporary interstellar dust stream for 200 days during the interplanetary cruise. Both collections present severe technical challenges in sample preparation and in analysis. By far the largest collection is the cometary one: approximately 300 micro g of material was returned from Wild 2, mostly consisting of approx. 1 ng particles embedded in aerogel or captured as residues in craters on aluminum foils. Because of their relatively large size, identification of the impacts of cometary particles in the collection media is straightforward. Reliable techniques have been developed for the extraction of these particles from aerogel. Coordinated analyses are also relatively straightforward, often beginning with synchrotron-based x-ray fluorescence (S-XRF), X-ray Absorption Near-Edge Spectoscopy (XANES) and x-ray diffraction (S-XRD) analyses of particles while still embedded in small extracted wedges of aerogel called ``keystones'', followed by ultramicrotomy and TEM, Scanning Transmission X-ray Microscopy (STXM) and ion microprobe analyses (e.g., Ogliore et al., 2010). Impacts in foils can be readily analyzed by SEM-EDX, and TEM analysis after FIB liftout sample preparation. In contrast, the interstellar dust collection is vastly more challenging. The sample size is approximately six orders of magnitude smaller in total mass. The largest particles are only a few pg in mass, of which there may be only approx.10 in the entire collection. The technical challenges, however, are matched by the scientific importance of the collection. We formed a consortium carry out the Stardust Interstellar Preliminary Examination (ISPE) to carry out an assessment of this collection, partly in order to characterize the collection in sufficient detail so that future investigators could make well-informed sample requests. The ISPE is the sixth PE on extraterrestrial collections carried out with NASA support. Some of the basic questions that we asked were: how many impacts are there in the collector, and what fraction of them have characteristics consistent with extraterrestrial materials? What is the elemental composition of the rock-forming elements? Is there crystalline material? Are there organics? Here we present coordinated microanalyses of particles captured in aerogel, using S-FTIR, S-XRF, STXM, S-XRD; and coordinated microanalyses of residues in aluminum foil, using SEMEDX, Auger spectroscopy, STEM, and ion microprobe. We discuss a novel approach that we employed for identification of tracks in aerogel, and new sample preparation techniques developed during the ISPE. We have identified seven particles - three in aerogel and four in foils - that are most consistent with an interstellar origin. The seven particles exhibit a large diversity in elemental composition. Dynamical evidence, supported supported by laboratory simulations of interstellar dust impacts in aerogel and foils, and numerical modeling of interstellar dust propagation in the heliosphere, suggests that at least some of the particles have high optical cross-section, perhaps due to an aggregate structure. However, the observations are most consistent with a variety of morphologies

Westphal, Andrew J.↗

Final Reports of the Stardust ISPE: Seven Probable Interstellar Dust Particles

The Stardust spacecraft carried the first spaceborne collector specifically designed to capture and return a sample of contemporary interstellar dust to terrestrial laboratories for analysis [1]. The collector was exposed to the interstellar dust stream in two periods in 2000 and 2002 with a total exposure of approximately 1.8 10(exp 6) square meters sec. Approximately 85% of the collector consisted of aerogel, and the remainder consisted of Al foils. The Stardust Interstellar Preliminary Examination (ISPE) was a consortiumbased effort to characterize the collection in sufficient detail to enable future investigators to make informed sample requests. Among the questions to be answered were these: How many impacts are consistent in their characteristics with interstellar dust, with interplanetary dust, and with secondary ejecta from impacts on the spacecraft? Are the materials amorphous or crystalline? Are organics detectable? An additional goal of the ISPE was to develop or refine the techniques for preparation, analysis, and curation of these tiny samples, expected to be approximately 1 picogram or smaller, roughly three orders of magnitude smaller in mass than the samples in other small particle collections in NASA's collections - the cometary samples returned by Stardust, and the collection of Interplanetary Dust Particles collected in the stratosphere.

Allen, Carlton↗

Stardust Interstellar Preliminary Examination III: Infrared Spectroscopic Analysis of Interstellar Dust Candidates

Under the auspices of the Stardust Interstellar Preliminary Examination, picokeystones extracted from the Stardust Interstellar Dust Collector were examined with synchrotron Fourier transform infrared (FTIR) microscopy to establish whether they contained extraterrestrial organic material. The picokeystones were found to be contaminated with varying concentrations and speciation of organics in the native aerogel, which hindered the search for organics in the interstellar dust candidates. Furthermore, examination of the picokeystones prior to and post X-ray microprobe analyses yielded evidence of beam damage in the form of organic deposition or modification, particularly with hard X-ray synchrotron X-ray fluorescence. From these results, it is clear that considerable care must be taken to interpret any organics that might be in interstellar dust particles. For the interstellar candidates examined thus far, however, there is no clear evidence of extraterrestrial organics associated with the track and/or terminal particles. However, we detected organic matter associated with the terminal particle in Track 37, likely a secondary impact from the Al-deck of the sample return capsule, demonstrating the ability of synchrotron FTIR to detect organic matter in small particles within picokeystones from the Stardust interstellar dust collector.

Interstellar↗

Constraining the Origin of Impact Craters on Al Foils from the Stardust Interstellar Dust Collector

Preliminary examination (PE) of the aerogel tiles and Al foils from the Stardust Interstellar Dust Collector has revealed multiple impact features. Some are most likely due to primary impacts of interstellar dust (ISD) grains, and others are associated with secondary impacts of spacecraft debris, and possibly primary impacts of interplanetary dust particles (IDPs) [1, 2]. The current focus of the PE effort is on constraining the origin of the individual impact features so that definitive results from the first direct laboratory analysis of contemporary ISD can be reported. Because crater morphology depends on impacting particle shape and composition, in addition to the angle and direction of impact, unique particle trajectories are not easily determined. However, elemental analysis of the crater residues can distinguish real cosmic dust from the spacecraft debris, due to the low cosmic abundance of many of the elements in the spacecraft materials. We present here results from the elemental analysis of 24 craters and discuss the possible origins of 4 that are identified as candidate ISD impacts

Stroud, Rhonda M.↗

Identification of Crystalline Material in Two Interstellar Dust Candidates from the Stardust Mission

NASA's interstellar collector from the Stardust mission captured several particles that are now thought to be of interstellar origin. We analyzed two of these via nanodiffraction at the European Synchrotron Radiation Facility (ESRF) and found them to contain crystalline components. The unit cell of the crystalline material is determined from the diffraction patterns and the most likely mineral components are identified as olivine and spinel.

Gainsforth, Zack↗

Microanalysis of Hypervelocity Impact Residues of Possible Interstellar Origin

The NASA Stardust spacecraft deployed two collector trays, one dedicated to the collection of dust from Comet Wild 2, and the other for the capture of interstellar dust (ISD). The samples were returned successfully to Earth in 2006, and now provide an unprecedented opportunity for laboratory-based microanalysis of materials from the outer solar system and beyond. Results from the cometary sample studies have demonstrated that Wild 2 contains much more refractory condensate material and much less pristine extra-solar material than expected, which further indicates that there was significant transport of inner solar system materials to the Kuiper Belt in the early solar system [1]. The analysis of the interstellar samples is still in the preliminary examination (PE) phase, due to the level of difficulty in the definitive identification of the ISD features, the overall low abundance, and its irreplaceable nature, which necessitates minimally invasive measurements [2]. We present here coordinated microanalysis of the impact features on the Al foils, which have led to the identification of four impacts that are possibly attributable to interstellar dust. Results from the study of four ISD candidates captured in aerogel are presented elsewhere [2].

Stroud, Rhonda M.↗

Organics Captured from Comet Wild 2 by the Stardust Spacecraft

Organics found in Comet Wild 2 samples show a heterogeneous and unequilibrated distribution in abundance and composition. Some are similar, but not identical, to those in interplanetary dust particles (IDPs) and carbonaceous meteorites. A new class of aromatic-poor organic material is also present. The organics are rich in O and N compared to meteoritic organics. Aromatic compounds are present, but the samples tend to be relatively poorer in aromatics than meteorites and IDPs. D and 15N suggest that some organics have an interstellar/protostellar heritage. While the variable extent of modification of these materials by impact capture is not yet fully constrained, a remarkably diverse suite of organic compounds is present and identifiable within the returned samples.

Sandford, Scott A.↗

SXRF determination of trace elements in chondrule rims in the unequilibrated CO3 chondrite, ALH A77307

The concentrations of Ni, Cu, Zn, Ga, Ge, and Se in five chondrule rims in the CO3 chondrite ALH A77307 (3.0) using the synchrotron x-ray fluorescence (SXRF) microprobe at Brookhaven National Laboratory were determined. The data show that the trace element chemistry of rims on different chondrules is remarkably similar, consistent with data obtained for the major elements by electron microprobe. These results support the idea that rims are not genetically related to individual chondrules, but all sampled the same reservoir of homogeneously mixed dust. Of the trace elements analyzed Zn and Ga show depletions relative to CI chondrite values, but in comparison with bulk CO chondrites all the elements are enriched by approximately 1.5 to 3.5 x CO. The high concentrations of the highly volatile elements Se and Ga and moderately volatile Zn (1.5 to 2 x CO) in rims show that matrix is the major reservoir of volatile elements in ALH A77307.

Brearley, Adrian J.↗