Silica coated hard-magnetic strontium hexaferrite nanoparticles

Stable colloids of hard magnetic particles are newly developed and very promising materials. Surface functionalization of these particles remains challenging because the particles tend to aggregate during reaction due to strong magnetic interactions. Herein we report on a synthesis of strontium hexaferrite hard magnetic nanoparticles coated with silica by hydrolysis of tetraethoxysilane. As a source of hexaferrite we used stable colloid of plate-like nanoparticles with mean diameter of 40 nm and thickness of 5 nm, which were prepared by a glass-ceramic process. We have shown that to successfully coat each hexaferrite particle individually the hydrolysis conditions should provide heterogeneous nucleation of silica with rate higher than the aggregation rate of the colloidal nanoparticles. The resulting materials represent single crystal hexaferrite cores wrapped in silica shell with mean thickness of 18 and 23 nm depending on synthesis conditions. The obtained core-shell particles can be easily dispersed as stable aqueous colloids. The materials can be used as magnetic sorbents or nanocontainers and, furthermore, they are very promising colloidal building blocks for various magnetically assembled nanostructures.     

Barrierless Free Charge Generation in the High-Performance PM6:Y6 Bulk Heterojunction Non-Fullerene Solar Cell

Organic solar cells are currently experiencing a second golden age thanks to the development of novel non-fullerene acceptors (NFAs). Surprisingly, some of these blends exhibit high efficiencies despite a low energy offset at the heterojunction. Herein, free charge generation in the high-performance blend of the donor polymer PM6 with the NFA Y6 is thoroughly investigated as a function of internal field, temperature and excitation energy. Results show that photocurrent generation is essentially barrierless with near-unity efficiency, regardless of excitation energy. Efficient charge separation is maintained over a wide temperature range, down to 100 K, despite the small driving force for charge generation. Studies on a blend with a low concentration of the NFA, measurements of the energetic disorder, and theoretical modeling suggest that CT state dissociation is assisted by the electrostatic interfacial field which for Y6 is large enough to compensate the Coulomb dissociation barrier.     

Organometallic ruthenium inhibitors of glutathione-S-transferase P1-1 as anticancer drugs

Ruthenium-arene complexes conjugated to ethacrynic acid were prepared as part of a strategy to develop novel glutathione-S-transferase (GST) inhibitors with alternate modes of activity through the organometallic fragment, ultimately to provide targeted ruthenium-based anticancer drugs. Enzyme kinetics and electrospray mass spectrometry experiments using GST P1-1 and its cysteine-modified mutant forms revealed that the complexes are effective enzyme inhibitors, but they also rapidly inactivate the enzyme by covalent binding at Cys 47 and, to a lesser extent, Cys 101. They are highly effective against the GST Pi-positive A2780 and A2780cisR ovarian carcinoma cell lines, are among the most effective ruthenium complexes reported so far, and target ubiquitous GST Pi overexpressed in many cancers.     

Differentiation of Fresh Greek Orange Juice of the Merlin Cultivar According to Geographical Origin Based on the Combination of Organic Acid and Sugar Content as well as Physicochemical Parameters Using Chemometrics

The aim of the present study was to differentiate fresh Greek orange juice prepared from the Merlin cultivar according to geographical origin, based on organic acid/sugar content, and physicochemical parameter analysis, using chemometrics. For this purpose, oranges were collected during the harvesting period 2013–2014 from four different regions in Greece where Merlin oranges are produced. The analysis of organic acids and sugars was performed using a modified high pressure liquid chromatographic (HPLC–DAD/RI) method. Applying MANOVA and LDA analysis to the collected data, orange juices were successfully classified according to geographical origin (correct classification rate 83.3%). For validation purposes of the applied model, oranges from the harvesting period 2014–2015 were also collected and new instrumental and chemometric analysis carried out involving orange juice from both harvesting periods. Cumulative results showed that the classification rate remained practically constant, recording a correct classification rate of 80.4%, confirming the discriminatory power of the applied model. In order to further improve the overall classification rate, physicochemical parameter data were subjected to chemometric analysis along with organic acid and sugar content data. Results showed that the combination of organic acids, sugars, and physicochemical parameters somewhat increased the overall correct prediction rate to 82.0%. Present results enhance the potential of multi-parameter analysis for the correct geographical differentiation of Greek fresh orange juice, aiding to product quality and authenticity control.     

New Hybrid Compounds Combining Fragments of Usnic Acid and Thioether Are Inhibitors of Human Enzymes TDP1, TDP2 and PARP1

Tyrosyl-DNA phosphodiesterase 1 (TDP1) catalyzes the cleavage of the phosphodiester bond between the tyrosine residue of topoisomerase 1 (TOP1) and the 3′ phosphate of DNA in the single-strand break generated by TOP1. TDP1 promotes the cleavage of the stable DNA–TOP1 complexes with the TOP1 inhibitor topotecan, which is a clinically used anticancer drug. This article reports the synthesis and study of usnic acid thioether and sulfoxide derivatives that efficiently suppress TDP1 activity, with IC₅₀ values in the 1.4–25.2 μM range. The structure of the heterocyclic substituent introduced into the dibenzofuran core affects the TDP1 inhibitory efficiency of the compounds. A five-membered heterocyclic fragment was shown to be most pharmacophoric among the others. Sulfoxide derivatives were less cytotoxic than their thioester analogs. We observed an uncompetitive type of inhibition for the four most effective inhibitors of TDP1. The anticancer effect of TOP1 inhibitors can be enhanced by the simultaneous inhibition of PARP1, TDP1, and TDP2. Some of the compounds inhibited not only TDP1 but also TDP2 and/or PARP1, but at significantly higher concentration ranges than TDP1. Leader compound 10a showed promising synergy on HeLa cells in conjunction with the TOP1 inhibitor topotecan.     

Photophysical Properties of BADAN Revealed in the Study of GGBP Structural Transitions

The fluorescent dye BADAN (6-bromoacetyl-2-dimetylaminonaphtalene) is widely used in various fields of life sciences, however, the photophysical properties of BADAN are not fully understood. The study of the spectral properties of BADAN attached to a number of mutant forms of GGBP, as well as changes in its spectral characteristics during structural changes in proteins, allowed to shed light on the photophysical properties of BADAN. It was shown that spectral properties of BADAN are determined by at least one non-fluorescent and two fluorescent isomers with overlapping absorbing bands. It was found that BADAN fluorescence is determined by the unsolvated “PICT” (planar intramolecular charge transfer state) and solvated “TICT” (twisted intramolecular charge transfer state) excited states. While “TICT” state can be formed both as a result of the “PICT” state solvation and as a result of light absorption by the solvated ground state of the dye. BADAN fluorescence linked to GGBP/H152C apoform is quenched by Trp 183, but this effect is inhibited by glucose intercalation. New details of the changes in the spectral characteristics of BADAN during the unfolding of the protein apo and holoforms have been obtained.     

Hematopoietic Disorders,Renal Impairment and Growth in Mucopolysaccharidosis-Plus Syndrome

Mucopolysaccharidoses (MPS) are rare lysosomal storage disorders (LSD) characterized by the excessive accumulation of glycosaminoglycans (GAG). Conventional MPS, caused by inborn deficiencies of lysosomal enzymes involved in GAG degradation, display various multisystemic symptoms—including progressive neurological complications, ophthalmological disorders, hearing loss, gastrointestinal and hepatobiliary issues, cardiorespiratory problems, bone and joint abnormalities, dwarfism, and coarse facial features. Mucopolysaccharidosis-Plus Syndrome (MPSPS), an autosomal recessive disease caused by a mutation in the endo-lysosomal tethering protein VPS33A, shows additional renal and hematopoietic abnormalities (“Plus symptoms”) uncommon in conventional MPS. Here, we analyze data from biochemical, histological, and physical examinations—particularly of blood counts and kidney function—to further characterize the clinical phenotype of MPSPS. A series of blood tests indicate hematopoietic symptoms including progressive anemia and thrombocytopenia, which correlate with histological observations of hypoplastic bone marrow. High urinary excretion of protein (caused by impairments in renal filtration), hypoalbuminemia, and elevated levels of creatinine, cholesterol, and uric acid indicate renal dysfunction. Histological analyses of MPSPS kidneys similarly suggest the extensive destruction of glomerular structures by foamy podocytes. Height and weight did not significantly deviate from the average, but in some cases, growth began to decline at around six months or one year of age.     

Combined effect of irradiation and modified atmosphere packaging on shelf-life extension of chicken breast meat: microbiological, chemical and sensory changes

In the present study the combined effect of gamma irradiation (2 and 4 kGy) and modified atmosphere packaging (MAP) (30% CO₂/70% N₂ and 70% CO₂/30% N₂) on shelf life extension of fresh chicken meat stored under refrigeration was investigated. The study was based on microbiological (TVC, Pseudomonas spp., Lactic Acid Bacteria, Yeasts, Brochothrix thermosphacta, Enterobacteriaceae), physicochemical (pH, TBA, color) and sensory (odor, taste) changes occurring in chicken samples. Microbial populations were reduced by 1–5 log cfu/g for a given sampling day depending on the specific treatment. The effect was more pronounced in the case of the combination of MAP (70% CO₂/30% N₂) and the higher irradiation dose of 4 kGy. Of the chemical indicators of spoilage, TBA values for all treatments remained lower than 1 mg malondialdehyde (MDA)/kg meat throughout the 25 day storage period. pH values varied between 6.4 (day 0) and 5.9 (day 25). The values of the color parameters L*, a* and b* were not considerably affected by MAP. Irradiation resulted in a small increase of the parameter a*. Irradiation had a greater effect in extending the shelf life of chicken as compared to MAP. Sensory evaluation showed that the combination of irradiation at 4 kGy and MAP (70% CO₂/30% N₂) resulted in the highest shelf-life extension by 12 days compared to the air packaged samples.