Combining atom‐transfer radical polymerization and ring‐opening polymerization through bifunctional initiators derived from hydroxy benzyl alcohol—Preparation and characterization of initiators,macroinitiators, and block copolymers

A simple, one‐step procedure has been developed for the preparation of bifunctional initiators capable of polymerizing monomers suitable for atom‐transfer radical polymerization (ATRP) and ring‐opening polymerization (ROP). These bifunctional initiators were employed for making narrow disperse poly(styrene) macroinitiators, which were subsequently used for the ROP of various lactides to yield poly(styrene‐block‐lactide) copolymers. Thermogravimetric analysis (TGA) of these block copolymers are interesting in that it shows a two‐step degradation curve with the first step corresponding to the degradation of poly(lactide) segment and the second step associated with the poly(styrene) segment of the block copolymer. This nature of the block copolymer makes it possible to estimate the block copolymer content by TGA in addition to the ¹H NMR spectroscopic analysis. Thus, this study for the first time highlights the possibility of making porous materials by thermal means which are otherwise obtained by base hydrolysis. The bifunctional initiators were prepared by the esterification of 3‐hydroxy, 4‐hydroxy, and 3,5‐dihydroxy benzyl alcohols with α‐bromoisobutyryl bromide and 2‐bromobutyryl bromide. A mixture of products was obtained, which were purified by column chromatography. The esterified benzyl alcohols were employed in the polymerization of styrene under copper (Cu)‐catalyzed ATRP conditions to yield macroinitiators with low polydispersity. These macroinitiators were subsequently used in the ROP of L ‐, DL ‐, and mixture of lactides. The formation of block copolymers was confirmed by gel permeation chromatography (GPC), spectroscopic and thermal characterizations. The molecular weight of the block copolymers was always higher than the macroinitiator, and the GPC chromatogram was symmetrical indicating the uniform initiation of ROP by the macroinitiators. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 102–116, 2008     

Some criteria for the applicability of synthetic standards for laser spectral analysis of refractories

Summary The applicability of a series of synthetic standards for laser local analysis of refractories has been determined on the basis of 4 criteria: homogeneity, equality of the form and size of the craters formed by the laser beam, densities and plasma clouds. The validity of these criteria has been checked by comparison of the results received by electrone microprobe area scanning and by shooting the same places with a laser beam and reading the results with the help of synthetic standards.

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Kriterien zur Anwendbarkeit synthetischer Standards für die Laser-Spektralanalyse von feuerfesten Materialien

Zusammenfassung Die Anwendbarkeit von synthetischen Standards für die Laser-Lokalanalyse von feuerfesten Materialien wurde auf Grund von 4 Kriterien beurteilt: Homogenität, Gleichheit von Form und Größe der vom Laserstrahl verursachten Krater, Dichten und Plasmawolken. Die Gültigkeit dieser Kriterien wurde durch Vergleich der erhaltenen Ergebnisse mit den mit Hilfe der Elektronenmikrosonde erzielten Resultaten geprüft.

     

Comparative analysis of Reaction-Diffusion Manifold based reduced models for Head-On- and Side-Wall-Quenching flames

In this study, multi-dimensional molecular transport phenomena during Flame-Wall-Interactions (FWI) and their effects on model reduction strategies are investigated. In order to access the problem, the standard configurations of a two-dimensional Side-Wall Quenching (SWQ) flame and a one-dimensional Head-On Quenching (HOQ) flame are used and compared. In the case of the SWQ configuration it is shown that the gradients of the species scatter significantly both in the physical space and in the state space. Moreover, the gradient vector of the specific enthalpy describing energy losses towards the wall is not aligned with the gradient vectors of the species, which can be considered as a typical case while a flame in application might approach to the wall at any arbitrary transversal direction. This observation motivates to take the gradients’ scattering and multi-dimensional transport phenomena into account during model reduction to describe reliably the quenching process.The Reaction-Diffusion Manifold (REDIM) method is applied in this work. The method allows to take into account multi-dimensional transport in a very generic way. In order to generate the REDIM, gradient estimates are approximated by using a Singular-Value Decomposition (SVD) of SWQ detailed gradients fields. Two-dimensional REDIMs for both cases are constructed and compared to each other. Different transport (diffusion) models are implemented to compare quantitatively the manifolds with HOQ and SOQ gradients estimates. The comparison shows that the differences between reduced models with varying transport models is significantly larger than the differences for varying configurations (multidimensional gradient estimates). This justifies the use of a relatively simple REDIM for more complicated geometries and configurations. This simplifies the treatment and model reduction procedure significantly for such complicated transient phenomena.     

From a Point Cloud to a Simulation Model—Bayesian Segmentation and Entropy Based Uncertainty Estimation for 3D Modelling

The 3D modelling of indoor environments and the generation of process simulations play an important role in factory and assembly planning. In brownfield planning cases, existing data are often outdated and incomplete especially for older plants, which were mostly planned in 2D. Thus, current environment models cannot be generated directly on the basis of existing data and a holistic approach on how to build such a factory model in a highly automated fashion is mostly non-existent. Major steps in generating an environment model of a production plant include data collection, data pre-processing and object identification as well as pose estimation. In this work, we elaborate on a methodical modelling approach, which starts with the digitalization of large-scale indoor environments and ends with the generation of a static environment or simulation model. The object identification step is realized using a Bayesian neural network capable of point cloud segmentation. We elaborate on the impact of the uncertainty information estimated by a Bayesian segmentation framework on the accuracy of the generated environment model. The steps of data collection and point cloud segmentation as well as the resulting model accuracy are evaluated on a real-world data set collected at the assembly line of a large-scale automotive production plant. The Bayesian segmentation network clearly surpasses the performance of the frequentist baseline and allows us to considerably increase the accuracy of the model placement in a simulation scene.     

Diversification of a β-Lactam Pharmacophore via Allylic C-H Amination: Accelerating Effect of Lewis Acid Co-Catalyst

This report describes the use of Pd(II)/bis-sulfoxide 1 catalyzed intra- and intermolecular allylic C-H amination reactions to rapidly diversify structures containing a sensitive β-lactam core similar to that found in the monobactam antibiotic Aztreonam. Pharmacologically interesting oxazolidinone, oxazinanone, and linear amine motifs are rapidly installed with predictable and high selectivities under conditions that use limiting amounts of substrate. Additionally, we demonstrate for the first time that intramolecular C-H amination processes may be accelerated using catalytic amounts of a Lewis acid co-catalyst [Cr(III)(salen)Cl 2].     

Basal Cell Carcinoma: What’s New Under the Sun

Basal cell carcinoma (BCC) is the most common skin cancer in white populations with an increasing incidence worldwide, thereby imposing an important public health problem. Its etiology is still unclear, but existing data indicate that the risk for BCC development is of multifactorial origin and results from the interplay of both constitutional and environmental factors. Yet, UV radiation (UVR) is believed to be the predominant causative risk factor in the pathogenesis of BCC. For years, BCC and squamous cell carcinoma (SCC) have been grouped together as “nonmelanoma skin cancer.” However, it seems that there are considerable biologic differences between BCC and SCC, and thus each type of epithelial cancer should be addressed separately. The present review provides an overview of the intriguing etiologic link of BCC with UVR and attempts a comprehensive review of recent epidemiologic and molecular evidence that supports this association.     

A study of the removal of selenite and selenate from aqueous solutions using a magnetic iron/manganese oxide nanomaterial and ICP-MS

Selenium (Se) is naturally occurring in the environment and is an essential nutrient in mammals. However, environmental Se can be increased to toxic levels through different industrial practices. The potential adsorption of the Se oxoanions, selenite and selenate, from aqueous solutions onto nanosynthesized MnFe₂O₄ was investigated using batch techniques and DRC-ICP-MS spectroscopy. The nanomaterial (NM) was laboratory synthesized through slow titration of a mixture of Fe²⁺ and Mn²⁺ ions. X-ray diffraction and Scherrer's equation were used to determine the phase of the material and crystallite size, respectively. The effects of pH, reaction time, competitive anions, and the adsorption capacity of the synthesized NM to bind selenite and selenate were investigated. The Langmuir isotherm was used to determine the binding capacity of the NM. Results showed that the phase of the nanomaterial was similar to Jacobsite with a size of 27.5 nm. Results also showed that the sorption of either 100 ppb of selenite or selenate was pH independent in the pH range 2 to 6 and occurred within 5 min of contact time. The introduction of Cl⁻ and NO₃⁻ anions individually added to solution had no significant effect on the sorption of either selenite or selenate. However, it was found that the addition of SO₄²⁻ had a competitive effect only on the sorption of selenate, first seen at 10 ppm and more pronounced at 100 ppm of SO₄²⁻. In the presence of 100 ppm of PO₄³⁻, the adsorption of selenate decreased to 87% while selenite sorption decreased to 20%. From the Langmuir isotherm equation it was determined that the nano-Jacobsite had a selenite and selenate binding capacity of 6573.76 and 769.23 mg Se/kg of NM, respectively.     

Oil phase evaporation-induced self-assembly of hydrophobic nanoparticles into spherical clusters with controlled surface chemistry in an oil-in-water dispersion and comparison of behaviors of individual and clustered iron oxide nanoparticles

We report a general method for preparing nanoparticle clusters (NPCs) in an oil-in-water emulsion system mediated by cetyl trimethylammonium bromide (CTAB), where previously only individual nanoparticles were obtained. NPCs of magnetic, metallic, and semiconductor nanoparticles have been prepared to demonstrate the generality of the method. The NPCs were spherical and composed of densely packed individual nanoparticles. The number density of nanoparticles in the oil phase was found to be critical for the formation, morphology, and yield of NPCs. The method developed here is scalable and can produce NPCs in nearly 100% yield at a concentration of 5 mg/mL in water, which is approximately 5 times higher than the highest value reported in the literature. The surface chemistry of NPCs can also be controlled by replacing CTAB with polymers containing different functional groups via a similar procedure. The reproducible production of NPCs with well-defined shapes has allowed us to compare the properties of individual and clustered iron oxide nanoparticles, including magnetization, magnetic moments, and contrast enhancement in magnetic resonance imaging (MRI). We found that, due to their collective properties, NPCs are more responsive to an external magnetic field and can potentially serve as better contrast enhancement agents than individually dispersed magnetic NPs in MRI.     

Validation of an LC/MS method for the determination of gemfibrozil in human plasma and its application to a pharmacokinetic study

Gemfibrozil, a fibric acid hypolipidemic agent, is increasingly being used in clinical drug–drug interaction studies as an inhibitor of drug metabolizing enzymes and drug transporters. The validation of a fast, accurate and precise LC/MS method is described for the quantitative determination of gemfibrozil in an EDTA‐anticoagulated human plasma matrix. Briefly, gemfibrozil was extracted from human plasma by an acetonitrile protein precipitation method. The assay was reproducible with intra‐assay precision between 1.6 and 10.7%, and inter‐assay precision ranging from 4.4 to 7.8%. The assay also showed good accuracy, with intra‐assay concentrations within 85.6–108.7% of the expected value, and inter‐assay concentrations within 89.4–104.0% of the expected value. The linear concentration range was between 0.5 and 50 µg/mL with a lower limit of quantitation of 0.5 µg/mL when 125 µL of plasma were extracted. This LC/MS method yielded a quick, simple and reliable protocol for determining gemfibrozil concentrations in plasma and is applicable to clinical pharmacokinetic studies. Copyright © 2010 John Wiley & Sons, Ltd.