Molecular Cluster Distribution in Sea Water Near the Wall: Antifouling Aspect

It was investigated how the “wall effect” influences the cluster distribution in water and 3.5 wt.% NaCl solution being in a glass cylinder. The cluster distribution in a mass assemble up to 2.2 million Dalton was determined in dependence on the distance to the wall at normal atmospheric pressure. The average cluster mass, the rate of collapsed and skeletal clusters and the number of cluster kinds depended on the distance to the wall and on stirring methods. In different liquid’s layers and at different distances to the wall, there were registered newly appearing clusters as well as disappearing ones especially, solvated clusters of ion pairs (SCIPs). Under non-stirring conditions, the base water cluster (H₂O)₁₂ and (NaCl·40H₂O)₂ are the most sensitive to the wall distance. Other SCIPs like dimers, tetramers and hexamers remain stable at stirring in the vessel center (12 rad/s) and don’t react to wall approaching however at cylinder rotation (8.9 rad/s) these SCIPs are sensitive to the wall. The wall nature, the distance to the wall and the constant magnetic field were concluded to influence the cluster distribution differently. Cluster properties were assumed to be applied by sea water living organisms for their navigation.     

Synthesis of functionalized arylpyridines and -pyrimidines by domino [4+2]/retro [4+2] cycloadditions of electron-rich dienes with alkynylpyridines and -pyrimidines

Aryl-substituted pyridines and pyrimidines were prepared by [4+2] cycloadditions of alkynyl-substituted pyridines and -pyrimidines with electron-rich dienes. The reactions proceed by formation of a bridged cycloadduct and subsequent thermal extrusion of ethylene. The pyridine moiety plays a crucial role for the success of the reaction.     

3-Methoxalylchromones--versatile reagents for the regioselective synthesis of functionalized 2,4'-dihydroxybenzophenones, potential UV-filters

The reaction of 1,3-bis-silyl enol ethers with 3-methoxalylchromones affords a great variety of functionalised 2,4'-dihydroxybenzophenones. These products are formed by a domino Michael/retro-Michael/Mukaiyama-aldol reaction. The synthesized compounds are promising candidates for the synthesis of the novel UV-A/B and UV-B filters.     

Selective molecular sequestration with concurrent natural product functionalization and derivatization: from crude natural product extracts to a single natural product derivative in one step

A resin-bound nitroso compound sequestered a single unexpected component from crude plant seed extracts. Several plants, including Piper nigrum, Eugenia caryophyllata, and Pimenta dioica, were extracted with organic solvent in the presence of a nitroso-containing resin. The nitroso resin selectively sequestered a single compound, β-caryophyllene, via a chemo- and regioselective ene reaction. The ene product was released from the resin, and proper selection of the solid-phase linker and cleavage cocktail allowed concomitant further transformation of the primary ene product to a novel functionalized polycycle. Preliminary studies indicate that the new hydroxylamine-containing natural product derivatives have antibiotic activity.     

Editorial of the Special Issue of MCAP: S4G Stochastic Geometry,Stereology and Spatial Statistics

Methodology and Computing in Applied Probability -     

Immunocytochemical Localization of XRCC1 and γH2AX Foci Induced by Tightly Focused Femtosecond Laser Radiation in Cultured Human Cells

To assess the prospects for using intense femtosecond laser radiation in biomedicine, it is necessary to understand the mechanisms of its action on biological macromolecules, especially on the informational macromolecule—DNA. The aim of this work was to study the immunocytochemical localization of DNA repair protein foci (XRCC1 and γH2AX) induced by tightly focused femtosecond laser radiation in human cancer A549 cells. The results showed that no XRCC1 or γH2AX foci tracks were observed 30 min after cell irradiation with femtosecond pulses of 10¹¹ W∙cm⁻² peak power density. An increase in the pulse power density to 2 × 10¹¹ W∙cm⁻² led to the formation of linear tracks consisting both of XRCC1 and γH2AX protein foci localized in the places where the laser beam passed through the cell nuclei. A further increase in the pulse power density to 4 × 10¹¹ W∙cm⁻² led to the appearance of nuclei with total immunocytochemical staining for XRCC1 and γH2AX on the path of the laser beam. Thus, femtosecond laser radiation can be considered as a tool for local ionization of biological material, and this ionization will lead to similar effects obtained using ionizing radiation.     

Radiochemical Synthesis of 4-[18F]FluorobenzylAzide and Its Conjugation with EGFR-Specific Aptamers

Central nervous system tumors related to gliomas are of neuroectodermal origin and cover about 30% of all primary brain tumors. Glioma is not susceptible to any therapy and surgical attack remains one of the main approaches to its treatment. Preoperative tumor imaging methods, such as positron emission tomography (PET), are currently used to distinguish malignant tissue to increase the accuracy of glioma removal. However, PET is lacking a specific visualization of cells possessing certain molecular markers. Here, we report an application of aptamers to enhancing specificity in imaging tumor cells bearing the epidermal growth factor receptor (EGFR). Glioblastoma is characterized by increased EGFR expression, as well as mutations of this receptor associated with active division, migration, and adhesion of tumor cells. Since 2021, EGFR has been included into the WHO classification of gliomas as a molecular genetic marker. To obtain conjugates of aptamers GR20 and GOL1-specific to EGFR, a 4-[¹⁸F]fluorobenzylazide radiotracer was used as a synthon. For the production of the synthon, a method of automatic synthesis on an Eckert & Ziegler research module was adapted and modified using spirocyclic iodonium ylide as a precursor. Conjugation of 4-[¹⁸F]fluorobenzylazide and alkyne-modified aptamers was carried out using Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) with/without the TBTA ligand. As a result, it was possible to obtain ¹⁸F-labelled conjugates with 97% radiochemical purity for [¹⁸F]FB-GR20 and 98% for [¹⁸F]FB-GOL1. The obtained conjugates can be used for further studies in PET analysis on model animals with grafted glioblastoma.     

Photolysis by UVA–Visible Light of TNT in Ethanolic,Aqueous-Ethanolic,and Aqueous Solutions According to Electrospray and Aerodynamic Thermal Breakup Droplet Ionization Mass Spectrometry

The mechanism of photolytic degradation of 2-4-6-trinitrotoluene (TNT) by UVA–visible light (>320 nm) in ethanolic, aqueous-ethanolic, and aqueous solutions was investigated by electrospray and aerodynamic thermal breakup droplet ionization mass-spectrometric analyses. For the photolysis, a DRK-120 mercury-quartz lamp was used. Products of the photolysis reaction were compared with known products of TNT transformation in the environment. Because the photochemistry of some compounds in alcohols (in contrast to aqueous solutions) features a transfer of electrons from the solvent to the light-excited compound, we believe that the efficiency of photolysis (polymerization) of TNT in ethanol and aqueous-ethanolic solutions is based on this mechanism.