Stereochemical effects in fragmentation of diastereoisomers of protected diethyl 1,2‐diamino‐alkylphosphonates

Diastereoisomers of diethyl 5‐substituted (2‐thioxo‐imidazolidin‐4‐yl)phosphonates, which can be regarded as protected diethyl 1,2‐diaminoalkylphosphonates, have been analyzed by electron ionization mass spectrometry. Significant differences in the fragmentation of cis‐ and trans‐diastereoisomers were found. The stereospecificity of the elimination of diethyl phosphonate and the loss of the diethoxyphosphoryl group were studied using specific labeled compounds and collision‐induced dissociation. The relative abundances of ions formed via these fragmentation processes can be used for differentiation of both diastereoisomers. Copyright © 2010 John Wiley & Sons, Ltd.     

Drone Brood Homogenate as Natural Remedy for Treating Health Care Problem: A Scientific and Practical Approach

Drone brood homogenate is a little-known bee product used in folk medicine to treat various health problems. It is a very nutritious milky substance with high content of nutrients: proteins, lipids, fatty acids, carbohydrates, vitamins (A, B, E and D), and minerals. Moreover, when collected on early stage of larvae development, it is, most of all, rich source of sex hormone (testosterone, progesterone and estradiol). Some beekeepers consider drone brood as a waste product, although in some countries they use it to fight Varroa. Meanwhile, in many scientific reports a curative effect of bee drone homogenate in treating urgent global health problems have been confirmed, including ovarian dysfunction in women and male infertility, thyroid and immunity disorders, as well as malnutrition in children. A few dietary supplements based on drone brood are available online. Many patents relating to drone brood-based dietary supplements have been filed in Russia, but their prevalence in EU countries is still limited. Further research is needed to fully recognize the pharmacological activity and increase the use of drone brood.     

Labeled vs. Label-Free Raman Imaging of Lipids in Endothelial Cells of Various Origins

Endothelial cells (EC) constitute a single layer of the lining of blood vessels and play an important role in maintaining cardiovascular homeostasis. Endothelial dysfunction has been recognized as a primary or secondary cause of many diseases and it manifests itself, among others, by increased lipid content or a change in the lipid composition in the EC. Therefore, the analysis of cellular lipids is crucial to understand the mechanisms of disease development. Tumor necrosis factor alpha (TNF-α)-induced inflammation of EC alters the lipid content of cells, which can be detected by Raman spectroscopy. By default, lipid detection is carried out in a label-free manner, and these compounds are recognized based on their spectral profile characteristics. We consider (3S,3′S)-astaxanthin (AXT), a natural dye with a characteristic resonance spectrum, as a new Raman probe for the detection of lipids in the EC of various vascular beds, i.e., the aorta, brain and heart. AXT colocalizes with lipids in cells, enabling imaging of lipid-rich cellular components in a time-dependent manner using laser power 10 times lower than that commonly used to measure biological samples. The results show that AXT can be used to study lipids distribution in EC at various locations, suggesting its use as a universal probe for studying cellular lipids using Raman spectroscopy. The use of labeled Raman imaging of lipids in the EC of various organs could contribute to their easier identification and to a better understanding of the development and progression of various vascular diseases, and it could also potentially improve their diagnosis and treatment.     

Direct Nanospectroscopic Verification of the Amyloid Aggregation Pathway

The aggregation pathways of neurodegenerative peptides determine the disease etiology, and their better understanding can lead to strategies for early disease treatment. Previous research has allowed modelling of hypothetic aggregation pathways. However, their direct experimental observation has been elusive owing to methodological limitations. Herein, we demonstrate that nanoscale chemical mapping by tip‐enhanced Raman spectroscopy of single amyloid fibrils at various stages of aggregation captures the fibril formation process. We identify changes in TERS/Raman marker bands for Aβ_1‐42, including the amide III band (above 1255 cm^?1 for turns/random coil and below 1255 cm^?1 for β‐sheet conformation). The spatial distribution of β‐sheets in aggregates is determined, allowing verification of a particular fibrillogenesis pathway, starting from aggregation of monomers to meta‐stable oligomers, which then rearrange to ordered β‐sheets, already at the oligomeric or protofibrillar stage.     

New thiourea organocatalysts and their application for the synthesis of 5-(1H-indol-3-yl)methyl-2,2-dimethyl-1,3-dioxane-4,6-diones a source of chiral 3-indoylmethyl ketenes

The stereoselective properties of modified thiourea organocatalysts were tested in the Friedel–Crafts alkylation of indole with 5-arylidene-2,2-dimethyl-1,3-dioxane-4,6-diones, which produces chiral 5-((1H-indol-3-yl)(aryl)methyl)-2,2-dimethyl-1,3-dioxane-4,6-diones. Based on a tentative reaction mechanism for ((S)-N-benzyl-2-(3-(3,5-bis(trifluoromethyl)phenyl)thioureido)-N,3,3-trimethylbutanamide organocatalysts, modifications were applied in four selected regions. Systematic structure-stereoselectivity relationship study allowed designing the best efficient organocatalyst for the investigated Friedel–Crafts alkylation of indole with 5-arylidene-2,2-dimethyl-1,3-dioxane-4,6-diones.     

Optimization and Verification of Droplet Digital PCR Even-Specific Methods for the Quantification of GM Maize DAS1507 and NK603

In recent years, digital polymerase chain reaction (dPCR), a new molecular biology technique, has been gaining in popularity. Among many other applications, this technique can also be used for the detection and quantification of genetically modified organisms (GMOs) in food and feed. It might replace the currently widely used real-time PCR method (qPCR), by overcoming problems related to the PCR inhibition and the requirement of certified reference materials to be used as a calibrant. In theory, validated qPCR methods can be easily transferred to the dPCR platform. However, optimization of the PCR conditions might be necessary. In this study, we report the transfer of two validated qPCR methods for quantification of maize DAS1507 and NK603 events to the droplet dPCR (ddPCR) platform. After some optimization, both methods have been verified according to the guidance of the European Network of GMO Laboratories (ENGL) on analytical method verification (ENGL working group on “Method Verification.” (2011) Verification of Analytical Methods for GMO Testing When Implementing Interlaboratory Validated Methods). Digital PCR methods performed equally or better than the qPCR methods. Optimized ddPCR methods confirm their suitability for GMO determination in food and feed.     

Optimisation of sample pre-treatment method for the determination of triclosan in marine sediments by high-performance liquid chromatography and marine benthic quality assessment in the southern Baltic Sea

This study comprises optimisation of sample preparation and HPLC analytical procedure for the determination of a personal care product ingredient, triclosan (TCS), in marine sediments. The testing of several varying pre-treatment parameters confirmed that ultrasonic extraction is an effective method for the isolation of TCS from marine sediments, and that the choice of extraction solvent appeared to be of major importance. The selection of the mobile-phase composition and the absorption wavelength was made for the high-performance liquid chromatography analysis step. Based on the validated method, a preliminary assessment of the benthic ecosystem quality with regards to TCS contamination has been demonstrated in the southern Baltic Sea – a semi-enclosed sea, characterised by poor water exchange, thus particularly susceptible to anthropopression. TCS has been identified and quantified in situ in marine bottom sediments, sediment dwelling isopod – Saduria entomon L. and estimated in silico in pore waters based on the equilibrium partition theory in order to assess the potential exposure and uptake from the aqueous phase. TCS concentrations identified in the bottom sediments of the Gdansk Basin, as the natural habitat for studied S.entomon L., appear to be threatening to the benthic environment. Particularly when considering S. entomon L. as a major nutrition source for cod (Gadus morhua) undergoing the feminisation process, since the recent studies prove TCS to have a potential to induce critical alterations in the endocrine system of marine ichthyofauna.     

Reversible adsorption of spherical particles from binary mixtures: long-time behaviour

Formation of monolayers of spherical particles in processes with reversible adsorption from mixtures of large and small particles was simulated in computer experiments. Computer program was based on an algorithm that took into account random sequential adsorption, desorption and lateral diffusion of adsorbed particles (RSA–DLD model). Computer experiments were performed for systems with rate constants of particle adsorption at least 10³ times higher than rate constants of desorption. In processes with very fast adsorption and slow desorption, formation of monolayer can be divided into two stages. During the first stage, the total surface coverage (the coverage with particles of both types) increases very fast and becomes very close to that at equilibrium. During the second stage, the total coverage changes very slowly and the system approaches equilibrium mainly by the replacement of large particles with the small ones. A simple kinetic model for evolution of the monolayer composition during the second stage has been proposed. Kinetic equations related to this model allow the determination of large particles’ desorption rate constants on the basis of changes in the surface concentrations of adsorbed large and small microspheres. The validity of the model has been tested comparing large particles’ desorption rate constants values that had been used for simulations with values of the corresponding rate constants determined using analytical equations, with a view to analysing the simulation results. To cite this article: S. Slomkowski et al., C. R. Chimie 6 (2003).