Overcoming the boundary effects in surface spline interpolation

Surface spline interpolation when the domain is all of R^d isknown to converge much faster to the data function f than inthe case when the domain is the unit ball. This difference isunderstood to be due to boundary effects which, as will be shown,also affect the size of the surface spline's coefficients. Wepropose a modified form of surface spline interpolation which,to a great extent, overcomes these boundary effects. This modifiedsurface spline interpolant uses only the values of f at thegiven interpolation points.     

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.     

ALS-associated mutant SOD1<Superscript>G93A</Superscript> causes mitochondrial vacuolation by expansion of the intermembrane space and by involvement of SOD1 aggregation and peroxisomes

Background  

Amyotrophic lateral sclerosis (ALS) is an age-dependent neurodegenerative disease that causes motor neuron degeneration, paralysis and death. Mutations in Cu, Zn superoxide dismutase (SOD1) are one cause for the familial form of this disease. Transgenic mice expressing mutant SOD1 develop age-dependent motor neuron degeneration, skeletal muscle weakness, paralysis and death similar to humans. The mechanism whereby mutant SOD1 induces motor neuron degeneration is not understood but widespread mitochondrial vacuolation has been observed during early phases of motor neuron degeneration. How this vacuolation develops is not clear, but could involve autophagic vacuolation, mitochondrial permeability transition (MPT) or uncharacterized mechanisms. To determine which of these possibilities are true, we examined the vacuolar patterns in detail in transgenic mice expressing mutant SOD1^G93A.     

Dichlorocarbene Addition to

In contrast to the terminal phosphinidene complex PhPW(CO)(5) (2), which adds to [5]metacyclophane (1) in a 1,4-fashion, dichlorocarbene preferentially adds in a 1,2-fashion to the formal "anti-Bredt" type double bond of the aromatic ring of 1 to afford the norcaradiene 11b, which immediately rearranges to the bridged cycloheptatriene 12b and further by a [1,5] sigmatropic chlorine migration to the isomeric 13b as the first observable product. More slowly, the latter isomerizes via a dissociative mechanism to give 15b. A computational study supports the notion that the [1,5] chlorine migration in the rearrangement 12b --> 13b, for which an activation barrier of 70.2 kJ mol(-)(1) was calculated, is essentially concerted with minor charge separation. In contrast, the analogous [1,5] chlorine migration in the flat model compound 7,7-dichlorocycloheptatriene (12a) displays features of a dissociative pathway.