Coexistence results for catalysts

Summary In this paper we consider a modification of Ziff, Gulari and Barshad's (1986) model of oxidation of carbon monoxide on a catalyst surface in which the reactants are mobile on the catalyst surface. We find regions in the parameter space in which poisoning occurs (the catalyst surface becomes completely occupied by one type of atom) and another in which there is a translation invariant stationary distribution in which the two atoms have positive density. The last result is proved by exploiting a connection between the particle system with fast stirring and a limiting system of reaction diffusion equations.     

Bielliptic surfaces as covers of rational surfaces

We present a construction of the bielliptic surfaces as covers of certain rational elliptic surfaces.     

Quantitative mass spectrometry in proteomics: a critical review

The quantification of differences between two or more physiological states of a biological system is among the most important but also most challenging technical tasks in proteomics. In addition to the classical methods of differential protein gel or blot staining by dyes and fluorophores, mass-spectrometry-based quantification methods have gained increasing popularity over the past five years. Most of these methods employ differential stable isotope labeling to create a specific mass tag that can be recognized by a mass spectrometer and at the same time provide the basis for quantification. These mass tags can be introduced into proteins or peptides (i) metabolically, (ii) by chemical means, (iii) enzymatically, or (iv) provided by spiked synthetic peptide standards. In contrast, label-free quantification approaches aim to correlate the mass spectrometric signal of intact proteolytic peptides or the number of peptide sequencing events with the relative or absolute protein quantity directly. In this review, we critically examine the more commonly used quantitative mass spectrometry methods for their individual merits and discuss challenges in arriving at meaningful interpretations of quantitative proteomic data.     

Scaling Platinum-Catalyzed Hydrogen Dissociation on Corrugated Surfaces

We determine absolute reactivities for dissociation at low coordinated Pt sites. Two curved Pt(111) single-crystal surfaces allow us to probe either straight or highly kinked step edges with molecules impinging at a low impact energy. A model extracts the average reactivity of inner and outer kink atoms, which is compared to the reactivity of straight A- and B-type steps. Local surface coordination numbers do not adequately capture reactivity trends for H₂ dissociation. We utilize the increase of reactivity with step density to determine the area over which a step causes increased dissociation. This step-type specific reactive area extends beyond the step edge onto the (111) terrace. It defines the reaction cross-section for H₂ dissociation at the step, bypassing assumptions about contributions of individual types of surface atoms. Our results stress the non-local nature of H₂ interaction with a surface and provide insight into reactivity differences for nearly identical step sites.     

Pulse‐shape instabilities and their measurement

Multi‐shot pulse‐shape measurements of trains of ultrashort pulses with unstable pulse shapes are studied. Measurement techniques considered include spectral‐phase interferometry for direct electric‐field reconstruction (SPIDER), second harmonic generation frequency‐resolved optical gating (FROG), polarization gate FROG, and cross‐correlation FROG. An analytical calculation and simulations show that SPIDER cannot see unstable pulse‐shape components and only measures the coherent artifact. Further, the presence of this instability cannot be distinguished from benign misalignment effects in SPIDER. FROG methods yield a better, although necessarily rough, estimate of the pulse shape and also indicate instability by exhibiting disagreement between measured and retrieved traces. Only good agreement between measured and retrieved FROG traces or 100% SPIDER fringe visibility guarantees a stable pulse train.     

Vitamin D status of adults from tropical Australia determined using two different laboratory assays: implications for public health messages

We measured serum 25 hydroxyvitamin D [25(OH)D] levels of ambulatory adults in tropical Australia to determine whether it is appropriate to continue promoting sun‐safety in this population. In August 2006 (winter), self‐administered questionnaires were completed by 145 Meals‐on‐Wheels volunteers (49.3% male; mean age 57.8 ± 14.7 years; 76.6% response) from Townsville, Queensland (Latitude 19^oS). Serum 25(OH)D was analyzed using two common assays. Mean levels were 68.3 (SD ± 18.7; range 26–142) by DiaSorin Radioimmunoassay and 83.0 (SD ± 30.8; range 30–184) by DiaSorin Liaison^® one. No participants were 25(OH)D deficient (<25 nmol L⁻¹). Nine participants (6.2%) had 25(OH)D levels between 25 and 50 nmol L⁻¹ (insufficient), by both methods (seven with a BMI ≥ 25). Twenty‐eight participants (19.3%) had one result in the insufficient range and the other in the adequate range. Thus, almost all of these free‐living adults in tropical Australia had adequate vitamin D levels at the end of winter. There was poor agreement between the two 25(OH)D assays. These results suggest it is appropriate to continue promoting sun‐safe messages to the ambulatory Caucasian adult population of North Queensland, which has an extremely high incidence of skin cancer. The lack of agreement between the two assays is a concern. Few doctors are aware of this measurement issue.     

Synthesis of 2-iodoynamides and regioselective [2+2] cycloadditions with ketene

The first synthesis of 2-iodoynamides is described as well as the first [2+2] cycloadditions of ketene with iodo alkynes.     

Methodology for and the determination of the major constituents and metabolites of the Amazonian botanical medicine ayahuasca in human urine

Ayahuasca, also known as caapi or yage among various South American groups, holds a highly esteemed and millennia-old position in these cultures' medical and religious pharmacopeia. There is now an increasing interest in the potential for modern medical applications of ayahuasca, as well as concerns regarding its increasing potential for abuse. Toxicological and clinical research to address these issues will require information regarding its metabolism and clearance. Thus, a rapid, sensitive and specific method for characterization and quantitation of the major constituents and of the metabolites of ayahuasca in urine is needed. The present research provides a protocol for conducting such analyses. The characteristics of the method, conducted by sample dilution and using HPLC-electrospray ionization (ESI)-selected reaction monitoring (SRM)-tandem mass spectrometry, are presented. The application of the analytical protocol to urine samples collected from three individuals that were administered ayahuasca has also been demonstrated. The data show that the major metabolite of the hallucinogenic component of ayahuasca, N,N-dimethyltryptamine (DMT), is the corresponding N-oxide, the first time this metabolite has been described in in vivo studies in humans. Further, very little DMT was detected in urine, despite the inhibition of monoamine oxidase afforded by the presence of the harmala alkaloids in ayahuasca. The major harmala alkaloid excreted was tetrahydroharmine. Other excretion products and metabolites were also identified and quantified. The method described would be suitable for use in further toxicological and clinical research on ayahuasca.     

Versatile grafting approaches to star-shaped POSS-containing hybrid polymers using RAFT polymerization and click chemistry

An alkyne-bearing polyhedral oligomeric silsesquioxane (POSS) core was used to prepare POSS-containing polymer hybrids using 'grafting to' or 'grafting from' strategies in combination with reversible chain transfer and click chemistry.     

Simultaneous quantitation of testosterone and estradiol in human cell line (H295R) by liquid chromatography/positive atmospheric pressure photoionization tandem mass spectrometry

The possible interaction of environmental contaminants with the endocrine system has been an environmental concern since the early 1990s. To examine these interactions test guidelines have been introduced by regulatory agencies to screen for possible endocrine active compounds. One of these guidelines is the EPA's OPPTS 890.1550 [Steroidogenesis (Human Cell Line‐H295R)]. This guideline requires the quantification of two major biomarkers (testosterone and estradiol) in various biological test systems. Traditional quantitation methodologies such as Radioimmunoassay (RIA) and Enzyme‐linked Immunosorbent Assay (ELISA) have been used to quantify low levels of steroids. However, those methodologies have drawbacks such as the radioactive safety, antibody availability, separate assay for each biomarker, and lack of selectivity. In the current study, a rapid and sensitive liquid chromatography/positive atmospheric pressure photoionization tandem mass spectrometry method (LC/APPI‐MS/MS) has been developed and validated for the simultaneous quantitation of testosterone and estradiol in the H295R cell line. Briefly, the media from cultured cells was extracted with dichloromethane (CH₂Cl₂) containing internal standards of both testosterone‐d₃ and estradiol‐¹³C₃; then, the extracted organic layer was concentrated down to dryness. The final residue was derivatized with dansyl chloride solution, and directly analyzed by LC/APPI‐MS/MS. The calibration curves, with concentration ranging from 10 to 2500 pg/mL, were linear with coefficient >0.99. The lower limits of quantitation for both testosterone and estradiol were 10 pg/mL. This method was successfully validated to support requirements of the current EPA Steroidogenesis guideline. This type of method may also provide value for rapid and precise measurements of these two hormones in other in vitro or in vivo test systems. Copyright © 2011 John Wiley & Sons, Ltd.