Integrating 3D images using laboratory‐based micro X‐ray computed tomography and confocal X‐ray fluorescence techniques

The application of non‐destructive imaging to characterizing samples has become more important as the costs of samples increase. Imaging a sample via X‐ray techniques is preferable when altering or even touching the sample affects its properties, or when the sample is fielded after characterization. Two laboratory‐based X‐ray techniques used at Los Alamos include micro X‐ray computed tomography (MXCT) and confocal micro X‐ray fluorescence (confocal MXRF). Both methods create a 3D rendering of the sample non‐destructively. MXCT produces a high‐resolution (sub‐µm voxel) rendering of the sample based upon X‐ray absorption; the resulting model is a function of density and does not contain any elemental information. Confocal MXRF produces an elementally specific 3D rendering of the sample, but at a lower (30 × 30 × 65 µm) resolution. By combining data from these two techniques, scientists provided a more comprehensive method of analysis. We will describe a MATLAB routine written to render each of these data sets individually and/or within the same coordinate system. This approach is shown in the analysis of two samples: an integrated circuit surface mounted resistor and a machined piece of polystyrene foam. The samples chosen provide an opportunity to compare and contrast the two X‐ray techniques, identify their weaknesses and show how they are used in a complementary fashion. Copyright © 2010 John Wiley & Sons, Ltd.     

Formation of isoprostane bicyclic endoperoxides from the autoxidation of cholesteryl arachidonate

Autoxidation of polyunsaturated fatty acids and esters leads to a complex mixture containing hydroperoxides and cyclic peroxides. Prostaglandin bicyclic endoperoxides have been detected from the autoxidation of cholesteryl arachidonate by LC-MS and GC-MS techniques. All four possible types (I-IV) of bicyclic endoperoxides have been found starting from different regioisomeric hydroperoxides of cholesteryl arachidonate. Furthermore, the stereochemistry of Type IV bicyclic endoperoxides has been determined by conversion to pentafluorobenzyl (PFB) ester, trimethylsilyl (TMS) derivatives, and comparison with synthetic standards by the use of GC-MS. All eight possible diastereomers of the derivatized isoprostanes were observed and were separated by gas chromatography. The bicyclic endoperoxides with the two alkyl chains syn on the cyclopentane ring were formed preferentially to those with anti configuration, a result anticipated from earlier work. Substantial amounts of the anti-substituted isoprostanes, including PGF(2)(alpha), were, however, observed in the product mixture.     

Micro-X-ray fluorescence as a general high-throughput screening method for catalyst discovery and small molecule recognition

A powerful high-throughput screening technique is described for the rapid screening of bead-based libraries for catalyst discovery and molecular recognition. Micro-X-ray fluorescence (MXRF) screens materials for elemental composition with mesoscale analysis. This method is nondestructive and requires minimal sample preparation and no special tags for analysis, and the screening time is dependent on the desired sensitivity. The speed, sensitivity, and simplicity of MXRF as a high-throughput screening technique were applied to screen bead-based libraries of oligopeptides for phosphate hydrolysis catalysts and molecular recognition of selective receptors for the degradation products and analogues of chemical warfare agents. This paper demonstrates the analytical or HTS capability of MXRF for combinatorial screening. It is meant only to show the capabilities of MXRF and is not meant as an exhaustive study of the catalyst and molecular recognition systems presented.     

Picoliter solution deposition for total reflection X-ray fluorescence analysis of semiconductor samples

A deposition system capable of delivering picoliter quantities of solution in programmable arrays was investigated as a method for sample preparation for total reflection X-ray fluorescence (TXRF) spectroscopy. Arrays of trace metals in solution were deposited on Si wafers. The array deposits provide a capability of depositing closely spaced (100 μm or less), typically 5–20 μm diameter droplets in an area that can be matched to the analysis spot of the TXRF detector. The dried depositions were physically characterized and the effect of deposition type and matrix on the TXRF signal was investigated.     

Enhanced material classification using turbulence-degraded polarimetric imagery

An enhanced material-classification algorithm using turbulence-degraded polarimetric imagery is presented. The proposed technique improves upon an existing dielectric/metal material-classification algorithm by providing a more detailed object classification. This is accomplished by redesigning the degree-of-linear-polarization priors in the blind-deconvolution algorithm to include two subclasses of metals--an aluminum group classification (includes aluminum, copper, gold, and silver) and an iron group classification (includes iron, titanium, nickel, and chromium). This new classification provides functional information about the object that is not provided by existing dielectric/metal material classifiers. A discussion of the design of these new degree-of-linear-polarization priors is provided. Experimental results of two painted metal samples are also provided to verify the algorithm's accuracy.     

Energy spectra for decaying 2D turbulence in a bounded domain

We use results derived in the framework of the replica approach to study the liquid-glass thermodynamic transition. The main results are derived without using replicas and applied to the study of the Lennard-Jones binary mixture introduced by Kob and Andersen. We find that there is a phase transition due to the entropy crisis. We compute both analytically and numerically the value of the phase transition point T(K) and the specific heat in the low temperature phase.     

Mössbauer, NMR and ATR-FTIR spectroscopic investigation of degradation in RTV siloxane foams

The combination of experimental techniques allowed for a comprehensive study of aging processes occurring in RTV siloxane foams. ¹¹⁹Sn Mössbauer spectroscopy demonstrated that tin residues are composed of Sn(II) and Sn(IV) species. The 27-year-old foams showed only Sn(IV) species with a quadrupole-splitting parameter larger than that observed for SnO₂. Solid-state ²⁹Si NMR differentiated between the various functional linkages in the foams, and showed no significant change of the di- to trifunctional linkage ratios. High-resolution NMR, on solvent extract of foams, showed the presence of water, catalyst, plasticizer, and some silicone oligomers. ATR-FTIR demonstrated changes near the surface of the foam when aged with water and with the presence of the tin catalyst. Gamma irradiation at a low dose had little effect on compression sets. The main changes observed for artificially aged and aged in service foams were related to the presence of the tin catalyst.     

A high throughput screening method for the selection of zeolites for binding cations

An effective high throughput screening technique is described for the rapid analysis of zeolites as binding agents for cationic sequestration.     

Analysis of unsaturated compounds by Ag+ coordination ionspray mass spectrometry: studies of the formation of the Ag+/lipid complex

Coordination ionspray mass spectrometry (CIS-MS) is a useful tool in the detection and identification of cholesterol ester and phospholipid hydroperoxides and diacyl peroxides. Extensive studies of a series of cholesterol esters using CIS-MS revealed the following: (1) Cholesterol esters with equal number of double bonds as the internal standard showed a linear relative response in the mass spectrometer while compounds with non-equal numbers of double bonds gave a nonlinear relative response. (2) Complex adducts containing cholesterol ester, silver ion, AgF, AgBF(4), and 2-propanoxide form when silver is in molar excess of cholesterol esters, reducing the [M + Ag](+) signal. (3) In a mixture of cholesterol esters where silver is limiting, Ch22:6 and Ch20:4 bind to silver at the expense of Ch18:2 and have a higher signal in the mass spectrometer. (4) In a mixture of cholesterol esters where silver concentration is twofold greater than total cholesterol ester concentration, Ch22:6 and Ch20:4 form large complex adducts more frequently than Ch18:2 and have a lower signal in the mass spectrometer.