Trace elements in nail polish as a source of contamination of nail clippings when used in epidemiological studies

Summary Trace elements were determined in 27 brands of nail polish using INAA so as to estimate the impact of nail polish remainders when using (finger, toe) nail clippings as a bioindicator for epidemiological studies. Fe was found to be present up to almost 1.7% in one brand. No unambiguous correlation between trace elements and color was established, though transparent polish has the lowest trace element concentrations. An estimate of the maximum effect (no removal of the paint) indicates that over-estimates of some trace element levels in nail with more than 200.000% may occur. This study showed that if nail clippings will be used to study trace elements, very high demands have to be set to the efficiency and selectivity of the cleaning procedure.     

Organische, mit Wasser nicht mischbare L?sungsmittel in der Flammenphotometrie

Zusammenfassung Es wurde der Einfluß des Lösungsmittels auf die Empfindlichkeit der flammenphotometrischen Kupferbestimmung bei 40 verschiedenen organischen Lösungsmitteln, in denen innerkomplexe Verbindungen des Kupfers mit organischen Verbindungen gelöst waren, untersucht. Aliphatische Ester und Ketone, sowie Phenylmethyläther, Benzol, Toluol und Xylol erwiesen sich als besonders geeignet. Bei der angewandten Versuchsanordnung ließ sich die Empfindlichkeit der Bestimmung hierdurch auf etwa das 40 fache derjenigen steigern, wie man sie beim Versprühen rein wäßriger Kupferlösungen erreicht.Unsere Arbeit wurde durch Gaben der Deutschen Forschungsgemeinschaft und des Verbandes der Chemischen Industrie — Fonds der Chemie — gefördert, wofür auch an dieser Stelle gedankt sei.     

Observation of a complex nanoscale magnetic structure in a hexagonal Fe monolayer

We have observed a novel magnetic structure in the pseudomorphic Fe monolayer on Ir(111). Using spin-polarized scanning tunneling microscopy we find a nanometer-sized two-dimensional magnetic unit cell. A collinear magnetic structure is proposed consisting of 15 Fe atoms per unit cell with 7 magnetic moments pointing in one and 8 moments in the opposite direction. First-principles calculations verify that such an unusual magnetic state is indeed lower in energy than all solutions of the classical Heisenberg model. We demonstrate that the complex magnetic structure is induced by the strong Fe-Ir hybridization.     

A Markov Chain Monte Carlo comparison of variance estimators for the sampling of particulate mixtures

During the sampling of particulate mixtures, samples taken are analyzed for their mass concentration, which generally has non‐zero sample‐to‐sample variance. Bias, variance, and mean squared error (MSE) of a number of variance estimators, derived by Geelhoed, were studied in this article. The Monte Carlo simulation was applied using an observable first‐order Markov Chain with transition probabilities that served as a model for the sample drawing process. Because the bias and variance of a variance estimator could depend on the specific circumstances under which it is applied, Monte Carlo simulation was performed for a wide range of practically relevant scenarios. Using the ‘smallest mean squared error’ as a criterion, an adaptation of an estimator based on a first‐order Taylor linearization of the sample concentration is the best. An estimator based on the Horvitz–Thompson estimator is not practically applicable because of the potentially high MSE for the cases studied. The results indicate that the Poisson estimator leads to a biased estimator for the variance of fundamental sampling error (up to 428% absolute value of relative bias) in case of low levels of grouping and segregation. The uncertainty of the results obtained by the simulations was also addressed and it was found that the results were not significantly affected. The potentials of a recently described other approach are discussed for extending the first‐order Markov Chain described here to account also for higher levels of grouping and segregation. Copyright © 2013 John Wiley & Sons, Ltd.     

Chemoselective Derivatization of Folded Synthetic Insulin Variants with Potassium Acyltrifluoroborates (KATs)

Synthetic folded insulin variants containing an ornithine‐hydroxylamine residue are readily modified in aqueous buffers by amide‐forming ligations with potassium acyltrifluoroborates (KATs). The synthetic insulin analogs were prepared by Fmoc‐SPPS, α‐ketoacid‐hydroxylamine (KAHA) ligation, and a prosthetic C‐peptide that delivers the correct disulfide pattern and allows facile incorporation at the B0 position of Glargine M2 of a new ornithine hydroxylamine protected with a photolabile group. The folded insulin is readily modified by photo‐deprotection followed by amide‐forming KAT ligation to give insulin variants labeled with dyes, lipids, and PEGs, as well as the formation of a covalent dimer.     

Synthesis of Polymers Containing Potassium Acyltrifluoroborates (KATs) and Post-polymerization Ligation and Conjugation

We report the synthesis of monomers for atom-transfer radical polymerization (ATRP) and a reversible addition-fragmentation chain transfer (RAFT) agent bearing trifluoroborate iminiums (TIMs), which are quantitatively converted into potassium acyltrifluoroborates (KATs) after polymerization. The resulting KAT-containing polymers are suitable for rapid amide-forming ligations for both post-polymerization modification and polymer conjugation. The polymer conjugation occurs rapidly, even under dilute (micromolar) aqueous conditions at ambient temperatures, thereby enabling the synthesis of a variety of linear and star-shaped block copolymers. In addition, we applied post-polymerization modification to the covalent linking of a photocaged cyclic antibiotic (gramicidin S) to the side chains of the KAT-containing copolymer. Cellular assays revealed that the polymer–antibiotic conjugate is biocompatible and provides efficient light-controlled release of the antibiotic on demand.