Ambient Molecular Analysis of Biological Tissue Using Low-Energy,Femtosecond Laser Vaporization and Nanospray Postionization Mass Spectrometry

Direct analysis of plant and animal tissue samples by laser electrospray mass spectrometry (LEMS) was investigated using low-energy, femtosecond duration laser vaporization at wavelengths of 800 and 1042 nm followed by nanospray postionization. Low-energy (<50 μJ), fiber-based 1042 nm LEMS (F-LEMS) allowed interrogation of the molecular species in fresh flower petal and leaf samples using 435 fs, 10 Hz bursts of 20 pulses from a Ytterbium-doped fiber laser and revealed comparable results to high energy (75–1120 μJ), 45 fs, 800 nm Ti:Sapphire-based LEMS (Ti:Sapphire-LEMS) measurements. Anthocyanins, sugars, and other metabolites were successfully detected and revealed the anticipated metabolite profile for the petal and leaf samples. Phospholipids, especially phosphatidylcholine, were identified from a fresh mouse brain section sample using Ti:Sapphire-LEMS without the application of matrix. These lipid features were suppressed in both the fiber-based and Ti:Sapphire-based LEMS measurements when the brain sample was prepared using the optimal cutting temperature compounds that are commonly used in animal tissue cryosections.

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Film characteristics of anodic oxidized AZ91D magnesium alloy by applied power

This study examined the film characteristics of an anodized AZ91D magnesium alloy by varying the direct current and pulse frequency conditions. In order to evaluate the effect of the pulse frequency on film formation, anodic oxidation was carried out by applying direct current and pulse current at a current density of 300 mA/cm². Compared with the sample groups treated with the direct current, a large number of small arcs were generated continuously on the film treated with the pulse current and the film formation rate was found to increase. Homogeneous and compact pores were formed with increasing frequency, and the rate of formation was increased rapidly to the arrival voltage. The film thickness increased and the surface roughness decreased with increasing anodic oxidation time at a fixed frequency of 125 Hz. However, treatment for more than 3 min led to decomposition of the oxidized film onto the previously formed film, which caused an increase in the number of cracks and pores within the film. The most uniform and smallest pores were acquired when the surface was anodized for 3 min at a current density and frequency of 300 mA/cm² and 125 Hz, respectively. X‐ray diffraction revealed the formation of MgO and Mg₂SiO₄ peaks, with a relative decrease in peak intensity for the MgO and Mg substrate. The Vickers hardness value was higher on the treated groups than on the untreated group, and the potentiodynamic polarization test revealed satisfactory corrosion resistance through a decrease in corrosion density and a large improvement in the corrosion potential. Copyright © 2009 John Wiley & Sons, Ltd.     

Slow joins of loopy games

This paper is concerned with two-person games of perfect information and no chance moves in which play may possibly never terminate. The slow join is a way of playing several such games simultaneously, so as to form a single compound game. Our analysis of the slow join is accomplished by extending the notion of the suspense function from games which satisfy the stopping condition to the onside of games which may continue indefinitely. The remoteness function is also employed in the analysis.     

A complete analysis of Black-White Hackendot

RecentlyÚlehla [1980] gave a complete analysis of an impartial two-person combinatorial game called Hackendot which was invented by von Neumann. In this note we consider a partizan (or unimpartial) variation of Hackendot. Úlehla's analysis uses the Sprague-Grundy theory for disjunctive sums of impartial games. Our analysis employs Conway's theory for disjunctive sums of partizan games, two certain “biased” ways of “adding” dyadic rationals, and the usual addition of numbers.     

Effect of intramolecular energy transfer on the rate of unimolecular isomerization: HCN --HNC

This paper reports calculations of the rate of isomerization of HCN - HCN based on the theory of Gary and Rice as extended by Zhao and Rice. The major task is to determine the effect of intramolecular energy transfer on the prediction of the rate of isomerization. Both the full three-dimensional (3D) system and the reduced two-dimensional (2D) system obtained from freezing CN bond at 1.159 A are analyzed to check the validity of the freezing bond approximation. Meanwhile, RRKM rates are calculated to test RRKM choice of the transition state by comparing to Gary-Rice three-state model. The comparison shows that the rates from 2D model and 3D model are differing up to 20% with 2D rates consistently larger. The intramolecular energy transfer modifies the isomerization rate for HCN system up to 30% that is modestly small by the expectation. The isomerization rate predicted from RRKM theory is greater than those of Gary-Rice three-state model theory up to 65%, and it overstimates the rates under all consider     

A novel synthetic route to chiral gamma-lactams from alpha-amino acids via Rh-catalyzed intramolecular C-H insertion

Highly functionalized gamma-lactams are key intermediates for the synthesis of numerous biologically significant natural products. We herein described the synthesis of various chiral gamma-lactams via intramolecular C-H insertion of alpha-diazo-alpha-(phenylsulfonyl)acetamides derived from alpha-amino acids, which possess various functional groups. The cyclizations were highly regio- and stereoselective to afford chiral gamma-lactam motifs in high yields.