Colloidal synthesis of Au nanoparticles using polyelectrolytes with 1,3,4-thiadiazole as reducing agents

Heterocyclic compounds are well known for their biological activity and coordination properties. Some heterocyclic compounds have been employed in the stabilization against coalescence of metallic nanoparticles in colloidal solutions, for example, tetrazole, triazole, and pyrazole. The aim of this work is to design new polyelectrolytes with heterocyclic pendant groups useful as reducing agents of Au³⁺ and as stabilizing agents for the synthesis of colloidal Au nanoparticles. Thus, polyelectrolytes with thiosemicarbazone and 1,3,4-thiadiazole pendant groups were used as reducing agents of Au³⁺ ions and stabilizing agents of Au nanoparticles. The voltammetry study of the polyelectrolytes showed that one with thiosemicarbazone pendant groups is the better reducing agent than polyelectrolytes with heterocyclic pendant groups. The polyelectrolytes can control the growth of the nanoparticles, obtaining structures with an average size of 9 nm. In this study, it was concluded that the nature of the heterocyclic group does not have an effect on the shape of nanoparticles and quasi-spherical nanoparticles were obtained with all polyelectrolytes. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47790.     

Cell-Based Optimization of Covalent Reversible Ketoamide Inhibitors Bridging the Unprimed to the Primed Site of the Proteasome β5 Subunit

The ubiquitin-proteasome system (UPS) is an established therapeutic target for approved drugs to treat selected hematologic malignancies. While drug discovery targeting the UPS focuses on irreversibly binding epoxyketones and slowly-reversibly binding boronates, optimization of novel covalent-reversibly binding warheads remains largely unattended. We previously reported α-ketoamides to be a promising reversible lead motif, yet the cytotoxic activity required further optimization. This work focuses on the lead optimization of phenoxy-substituted α-ketoamides combining the structure-activity relationships from the primed and the non-primed site of the proteasome β5 subunit. Our optimization strategy is accompanied by molecular modeling, suggesting occupation of P1′ by a 3-phenoxy group to increase β5 inhibition and cytotoxic activity in leukemia cell lines. Key compounds were further profiled for time-dependent inhibition of cellular substrate conversion. Furthermore, the α-ketoamide lead structure 27 does not affect escape response behavior in Danio rerio embryos, in contrast to bortezomib, which suggests increased target specificity.     

Preparation and characterization of a macroporous agarose monolith as a stationary phase in IMAC chromatography

A macroporous monolith used as stationary phase for the separation of biomolecules by immobilized metal ion affinity chromatography (IMAC), based on D5 agarose (D5) chemically modified was proposed. The characterization of physical properties was studied. Pressure drop was <0.4?MPa, being a very low value compared to other similar chromatographic supports. The adsorption/desorption process was carried out using bovine serum albumin (BSA) at pH 7.4 as a target protein. The monolith was re-used for 20 adsorption/desorption cycles and it was possible to verify that the average percentage of adsorption in all cycles was 89.65%. It was also possible to apply a model in order to obtain the kinetic adsorption constant (k_a), desorption constant (k_d) and equilibrium constant (K_e) by the proposed system. These results indicate that this system is governed by the adsorption process.     

Analysis of Damage on the Streptococcus mutans Immersed in Ozonated Water: Preliminary Study for Application as Mouth Rinse

Ozonated water has been demonstrated to induce significant results in terms of the elimination of microorganisms. The present study assessed the damage to Streptococcus mutans after exposure to ozonated water; the ozone generator was adjusted to provide an outlet concentration of 60 mg/L, the samples were submitted to different ozonation times 1, 2, 4, 6, and 10 mi. Scanning electron microscopy and atomic force images were obtained to identify damage to the bacteria, followed by reactive oxygen species (ROS) evaluation and microbial viability. The results showed a significant reduction in viability and the images evidenced the generation of gaps on the microbial wall and surface layer alterations. Ozone can induce significant damage to S. mutans, thus suggesting that the use of ozonated water to prevent carious lesion formation is extremely promising.     

Evaluation of Antioxidant Compounds and Total Sugar Content in a Nectarine [Prunus persica (L.) Batsch] Progeny

Epidemiological studies suggest that consumption of fruit rich in phenolic compounds is associated with health-protective effects due to their antioxidant properties. For these reasons quality evaluation has become an important issue in fruit industry and in breeding programs. Phytochemical traits such as total phenolics, flavonoids, anthocyanins, L-ascorbic acid, sugar content and relative antioxidant capacity (RAC) were analyzed over four years in flesh fruit of an F1 population "Venus" × "Big Top" nectarines. Other traits such as harvesting date, yield, fruit weight, firmness, soluble solids concentration (SSC), pH, titratable acidity (TA) and ripening index (RI) were also determined in the progeny. Results showed high variability among genotypes for all analyzed traits. Total phenolics and flavonoids showed significant positive correlations with RAC implying that both are important antioxidant bioactive compounds in peaches. We found genotypes with enhanced antioxidant capacity and a better performance than progenitors, and in consequence the best marketability.     

Phase and Rheological Behavior of Cetyldimethylbenzylammonium Salicylate (CDBAS) and Water

The temperature–composition phase diagram in the diluted region of the cationic surfactant cetyldimethylbenzylammonium salicylate/water system was studied with a battery of techniques. The Krafft temperature (T _k = 33 ± 1 °C) was measured by differential scanning calorimetry, polarizing microscopy, conductimetry, viscosimetry, and rheometry. The critical vesicle concentration (cvc, ~0.002 wt%) and a vesicle–micellar transition (cvm, ~0.005 wt%) was detected at a temperature of 35 °C. Below T _k and concentrations ≤2 wt%, a transparent solution is formed (I). Above 2–8.5 wt%, a lamellar (L₁) phase forms. At higher concentrations and up to 12 wt%, a second lamellar phase (L₂) is detected. From 12.4 to 15.5 wt%, an emulsion phase (E) is formed. Rheological dynamic measurements for the I phase indicate that the system exhibits a predominantly viscous behavior (G′ < G″) for concentrations lower than the overlap or entanglement concentration (C _e, ~0.75 wt%). At higher concentrations, wormlike micelles form and the elastic behavior predominates (G′ > G″). The elastic (G′) modulus collapses in a concentration–time master curve in the whole reduced frequencies range ωτ _c examined, whereas the viscous modulus (G″) collapses only at reduced frequencies lower than 0.1. Reduced stress plotted as a function of the reduced shear rate yields a good superposition of the curves at the different concentrations up to the onset of the non-linear behavior.     

Purity,quality and stability of Argentinean virgin olive oils

In this paper we evaluate the stability, purity and regulated quality composition of fatty acids and sterols (both physico‐chemical and sensory) of commercial Argentinean virgin olive oils in order to evaluate their acceptance on the world market. For this purpose, samples of the best known and most widely distributed oils in supermarkets located in Buenos Aires (Argentina) were acquired. After thoroughly analysing these samples, only 20% were considered to have an acceptable quality. However, some were excluded because of their high campesterol content, which could be an intrinsic characteristic of these oils. The most useful analytical parameter used to confirm authenticity was ECN‐42 R – ECN‐42 T, followed by wax content and 3.5 stigmastadienes. Only 24% of the extra‐virgin olive oil samples were classified as ‘extra‐virgin’ from the regulated quality viewpoint. The low oleic and high linolenic acid contents of the Argentinean virgin olive oils stand out when compared with European virgin olive oils. The oxidative stability values may be considered very low, indeed even lower than those obtained in Spanish virgin olive oils.     

Nondegradative additive manufacturing of medical grade copolyesters of high molecular weight and with varied elastic response

Although additive manufacturing through melt extrusion has become increasingly popular as a route to design scaffolds with complex geometries the technique if often limited by the reduction in molecular weight and the viscoelastic response when degradable aliphatic polyesters of high molecular weight are used. Here we use a melt extruder and fused filament fabrication printer to produce a reliable nondegradative route for scaffold fabrication of medical grade copolymers of L-lactide, poly(ε-caprolactone-co-L-lactide), and poly(L-lactide-co-trimethylene carbonate). We show that degradation is avoided using filament extrusion and fused filament fabrication if the process parameters are deliberately chosen based upon the rheological behavior, mechanical properties, and polymer composition. Structural, mechanical, and thermal properties were assessed throughout the process to obtain comprehension of the relationship between the rheological properties and the behavior of the medical grade copolymers in the extruder and printer. Scaffolds with a controlled architecture were achieved using high-molecular-weight polyesters exhibiting a large range in the elastic response causing negligible degradation of the polymers. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48550.