New C8-substituted caffeine derivatives as promising antioxidants and cytoprotective agents in human erythrocytes.

New structurally diverse groups of C8-substituted caffeine derivatives were synthesized and evaluated for their chemical and biological properties. Mass spectrometry, FT-IR, and NMR characterizations of these derivatives were performed. The cytotoxic activity of the derivatives was estimated in vitro using human red blood cells (RBC) and in silico pharmacokinetic studies. The antioxidant capacity of the compounds was analyzed using a ferrous ion chelating activity assay. The ability of the derivatives to protect RBC from oxidative damage, including the oxidation of hemoglobin to methemoglobin, was assessed using a water-soluble 2,2'-azobis(2-methyl-propionamidine) dihydrochloride (AAPH) as a standard inducer of peroxyl radicals. The level of intracellular oxidative stress was assessed using the fluorescent redox probe 2',7'-dichlorodihydrofluorescein diacetate (DCF-DA). The results indicate that all derivatives are biocompatible compounds with significant antioxidant and cytoprotective potential dependent on their chemical structure. In order to explain the antioxidant and cytoprotective activity of the derivatives, a mechanism of hydrogen atom transfer (HAT), radical adduct formation (RAF), or single electron transfer (SET), as well as the specific interactions of the derivatives with the lipid bilayer of RBC membrane, have been proposed. The results show that selected modifications of the caffeine molecule enhance its antioxidant properties, which expands our knowledge of the structure-activity relationship of caffeine-based cytoprotective compounds.

What Drives Caterpillar Guilds on a Tree: Enemy Pressure, Leaf or Tree Growth, Genetic Traits, or Phylogenetic Neighbourhood?

Communities of herbivorous insects on individual host trees may be driven by processes ranging from ongoing development via recent microevolution to ancient phylogeny, but the relative importance of these processes and whether they operate via trophic interactions or herbivore movement remains unknown. We determined the leaf phenology, trunk diameter, genotype, and neighbourhood of sessile oak trees (Quercus petraea), and sampled their caterpillar communities. We found that leaf development across a time period of days related to free-living caterpillars, which disappeared with leaf age. Tree growth across decades is related to increased parasitism rate and diversity of herbivores. The microevolution of oak trees across millennia is related to the abundance of leaf-mining casebearers, which is higher on more homozygous oaks. However, oak genome size was not important for any guild. In contrast to most previous studies, the phylogenetic distance of oaks from their neighbours measured in millions of years was associated with higher abundances of entire caterpillar guilds. Furthermore, on trees surrounded by only distantly related tree species, parasitism tended to be lower. Lower parasitism, in turn, was associated with higher abundances of codominant caterpillar species. Neighbourhoods and traits of trees were also related to community composition and diversity, but not to the average wingspans or specialization of species, consistent with the assembly of herbivore communities being driven by leaf traits and parasitism pressure on trees rather than by insect movement among trees. However, movement in rarer species may be responsible for concentration effects in more phylogenetically distant neighbourhoods. Overall, we suggest that the assembly of insects on a tree is mostly driven by trophic interactions controlled by a mosaic of processes playing out over very different time scales. Comparisons with the literature further suggest that, for oak trees, the consequences of growing amongst distantly related tree species may depend on factors such as geographic region and tree age.

Ligand-Sensitised LaF3 :Eu3+ and SrF2 :Eu3+ Nanoparticles and in Vitro Haemocompatiblity Studies.

Luminescent Ln3+ -doped nanoparticles (NPs) functionalised with the desired organic ligand molecules for haemocompatibility studies were obtained in a one-pot synthesis. Chelated aromatic organic ligands such as isophthalic acid, terephthalic acid, ibuprofen, aspirin, 1,2,4,5-benzenetetracarboxylic acid, 2,6-pyridine dicarboxylic acid and adenosine were applied for surface functionalisation. The modification of the nanoparticles is based on the donor-acceptor character of the ligand-nanoparticle system, which is an alternative to covalent functionalisation by peptide bonding as presented in our recent report. The aromatic groups of selected ligands absorb UV light and transfer their excited-state energy to the dopant Eu3+ ions in LaF3 and SrF2 NPs. Herein, we discuss the structural and spectroscopic characterisation of the NPs and the results of haemocompatibility studies. Flow cytometry analysis of the nanoparticles' membrane-binding is also presented.