Properties and performance of BaxSr1−xCo0.8Fe0.2O3−δ materials for oxygen transport membranes

The present paper discusses the oxygen transport properties, oxygen stoichiometry, phase stability, and chemical and mechanical stability of the perovskites (BSCF) and (SCF) for air separation applications. The low oxygen conductive brownmillerite phase in SCF is characterized using in-situ neutron diffraction, thermographic analysis and temperature programmed desorption but this phase is not present for BSCF under the conditions studied. Although both materials show oxygen fluxes well above 10 ml/cm²·min at T=1,273 K and pO₂=1 bar for self-supporting, 200 μm-thick membranes, BSCF is preferred as a membrane material due to its phase stability. However, BSCF’s long-term stable performance remains to be confirmed. The deviation from ideal oxygen stoichiometry for both materials is high: δ>0.6. The thermal expansion coefficients of BSCF and SCF are 24×10⁻⁶ and 30×10⁻⁶ K⁻¹, respectively, as determined from neutron diffraction data. The phenomenon of kinetic demixing has been observed at pO₂<10⁻⁵ bar, resulting in roughening of the surface and enrichment with alkaline earth metals. Stress–strain curves were determined and indicated creep behavior that induces undesired ductility at T=1,073 K for SCF. Remedies for mechanical and chemical instabilities are discussed.     

New mock theta conjectures Part I

In their paper “A survey of classical mock theta functions”, Gordon and McIntosh observed that the classical mock \(\theta \)-functions, including those found by Ramanujan, can be expressed in terms of two ‘universal’ mock \(\theta \)-functions denoted by \(g_{2}\) and \(g_{3}\). These identities are known as mock \(\theta \)-conjectures. The fifth- and seventh-order mock \(\theta \)-conjectures were proved by Dean Hickerson. In the survey paper the authors gave mock \(\theta \)-conjectures for the other mock \(\theta \)-functions and referred the proofs to a future paper with this title, listed in their references as [GM4]. The purpose of this paper is to prove these identities for the functions of orders 2 and 3.     

A mathematical model of hotspot condensed phase ignition in the presence of a competitive endothermic reaction

We consider the propagation of a combustion front resulting from the gasless combustion of a condensed state fuel. The propagation of the front, essentially a premixed laminar flame, is supported by an exothermic reaction subject to possible heat loss through a competitive endothermic reaction. The dynamics of the endothermic process inducing the heat loss strongly depend on the temperature and the local fuel concentration. Through an analysis based on high activation energy, the steady-state values of the final burnt temperature as well as the burning velocity are obtained, and the control parameters are identified. Using a linear perturbation method, we assess the stability of the propagating front and obtain a condition for oscillatory behaviour. The critical parameter values for the transition from steady to oscillatory burning speeds are identified. The results represent a generalization of those obtained by Matkowsky and Sivashinsky to include the effects of heat loss induced by a competitive endothermic reaction.     

Acyclic 1,4-stereocontrol via reductive 1,3-transpositions

One-pot reduction/allylic diazene rearrangement of lactic acid- and mandelic acid-derived alpha,beta-unsaturated tosyl hydrazones leads to 1,4-syn- or 1,4-anti-E-2-alkenyl arrays in high yield and diastereoselectivity. Either the syn or the anti diastereomer can be prepared by choosing the appropriate alkene stereoisomer of the hydrazone. The E-alkenes led to the 1,4-syn isomers, while the Z-alkenes led to the 1,4-anti isomers, both with > or =20:1 diastereoselectivity.     

Biocatalytically oligomerized epicatechin with potent and specific anti-proliferative activity for human breast cancer cells

Catechins, naturally occurring flavonoids derived from wine and green tea, are known to exhibit multiple health benefits. Epigallocatechin gallate (EGCG) is one of the most widely investigated catechins, but its efficacy in cancer therapy is still inconsistent and limited. The poor stability of EGCG has contributed to the disparity in the reported anti-cancer activity and other beneficial properties. Here we report an innovative enzymatic strategy for the oligomerization of catechins (specifically epicatechin) that yields stable, water-soluble oligomerized epicatechins with enhanced and highly specific anti-proliferative activity for human breast cancer cells. This one-pot oxidative oligomerization is carried out in ambient conditions using Horseradish Peroxidase (HRP) as a catalyst yielding water-soluble oligo(epicatechins). The oligomerized epicatechins obtained exhibit excellent growth inhibitory effects against human breast cancer cells with greater specificity towards growth-inhibiting cancer cells as opposed to normal cells, achieving a high therapeutic differential. Our studies indicate that water-soluble oligomeric epicatechins surpass EGCG in stability, selectivity and efficacy at lower doses.     

Fractional mass filtering as a means to assess circulating metabolites in early human clinical studies

Recent changes in the regulatory environment have led to a need for new methods to assess circulating human drug metabolites in early clinical studies with respect to their potential toxicological impact. The specific goals of such studies are to determine if the metabolites present in human plasma following administration of a drug candidate also are observed in plasma from the animal studies employed for preclinical toxicological evaluation, and to estimate corresponding exposure margins (animal:human) for the major metabolites. Until recently, the accepted best practice for the characterization of circulating drug metabolites utilized liquid chromatography/tandem mass spectrometry (LC/MS/MS)-based methodologies, in conjunction with authentic chemical standards, for the detection and quantitative analyses of metabolites predicted from both animal studies and experiments with human liver preparations in vitro. While this approach is satisfactory for anticipated biotransformation products, metabolites that were not expected to circulate in human plasma frequently escape detection. Current accurate mass instruments enable the use of the technique of fractional mass filtering to detect both expected and unexpected metabolites in a rapid, less resource-intensive and more robust manner. Application of this technology to several clinical development programs at Merck Research Laboratories has demonstrated the value of fractional mass filtering in the assessment of circulating drug metabolites in early clinical trials.     

Amperometric sensor for ethanol based on one-step electropolymerization of thionine-carbon nanofiber nanocomposite containing alcohol oxidase

Thionine had strong interaction with carbon nanofiber (CNF) and was used in the non-covalent functionalization of carbon nanofiber for the preparation of stable thionine-CNF nanocomposite with good dispersion. With a simple one-step electrochemical polymerization of thionine-CNF nanocomposite and alcohol oxidase (AOD), a stable poly(thionine)-CNF/AOD biocomposite film was formed on electrode surface. Based on the excellent catalytic activity of the biocomposite film toward reduction of dissolved oxygen, a sensitive ethanol biosensor was proposed. The ethanol biosensor could monitor ethanol ranging from 2.0 to 252 μM with a detection limit of 1.7 μM. It displayed a rapid response, an expanded linear response range as well as excellent reproducibility and stability. The combination of catalytic activity of CNF and the promising feature of the biocomposite with one-step non-manual technique favored the sensitive determination of ethanol with improved analytical capabilities.     

Determination of the active and inactive metabolites of prasugrel in human plasma by liquid chromatography/tandem mass spectrometry

Two fast and sensitive liquid chromatography/tandem mass spectrometry (LC/MS/MS)-based bioanalytical assays were developed and validated to quantify the active and three inactive metabolites of prasugrel. Prasugrel is a novel thienopyridine prodrug that is metabolized to the pharmacologically active metabolite in addition to three inactive metabolites, which directly relate to the formation and elimination of the active metabolite. After extraction and separation, the analytes were detected and quantified using a triple quadrupole mass spectrometer using positive electrospray ionization. The validated concentration range for the inactive metabolites assay was from 1 to 500 ng/mL for each of the three analytes. Additionally, a 5x dilution factor was validated. The interday accuracy ranged from -10.5% to 12.5% and the precision ranged from 2.4% to 6.6% for all three analytes. All results showed accuracy and precision within +/-20% at the lower limit of quantification and +/-15% at other levels. The validated concentration range for the active metabolite assay was from 0.5 to 250 ng/mL. Additionally, a 10x dilution factor was validated. The interbatch accuracy ranged from -7.00% to 5.98%, while the precision ranged from 0.98% to 3.39%. Derivatization of the active metabolite in blood with 2-bromo-3'-methoxyacetophenone immediately after collection was essential to ensure the stability of the metabolite during sample processing and storage. These methods have been applied to determine the concentrations of the active and inactive metabolites of prasugrel in human plasma.     

Spectroscopic analysis of bacterial biological warfare simulants and the effects of environmental conditioning on a bacterial spectrum

The ability to distinguish bacteria from mixed samples is of great interest, especially in the medical and defence arenas. This paper reports a step towards the aim of differentiating pathogenic endospores in situ, to aid any required response for hazard management using infrared spectroscopy combined with multivariate analysis. We describe a proof-of-principle study aimed at discriminating biological warfare simulants from common environmental bacteria. We also report an evaluation of multiple pre-processing techniques and subsequent differences in cross-validation of two pattern recognition models (Support Vector Machines and Principal Component–Linear Discriminant Analysis) for a six-class classification (bacterial classification). These classifications were possible with an average sensitivity of 88.0 and 86.9?%, and an average specificity of 97.6 and 97.5?% for the SVM and the PC-LDA models, respectively. Most spectroscopic models are built upon spectra from bacteria that have been specifically prepared for analysis by a particular method; this paper will comment upon the differences in the bacterial spectrum that occur between specific preparations when the bacteria have spent 30?days in the simulated weather conditions of a hot dry climate.