Impact of high-intensity ultrasound on physical properties and degree of oxidation of lipase modified menhaden oil with caprylic acid and/or stearic acid

The purpose of this research was to determine the effect of high-intensity ultrasound (HIU) on physical properties, degree of oxidation, and oxidative stability of structured lipids (SLs). Caprylic acid (C) and stearic acid (S) were incorporated into menhaden oil using Lipozyme® 435 lipase to obtain five samples: (1) LC 20 (menhaden oil with 20% of C), (2) LC 30 (menhaden oil with 30% C), (3) LS 20 (menhaden oil with 20% S), (4) LS 30 (menhaden oil with 30% S), and (5) Blend C (menhaden oil with 16.24% C and 13.04% S). Samples were crystallized for 90 min at the following temperatures: (1) LC 20 at 15.5°C, (2) LC 30 at 17.5°C, (3) LS 20 at 24°C, (4) LS 30 at 30°C, and (5) Blend C at 18.0°C, and HIU was applied at the onset of crystallization. Physical properties, degree of oxidation, and oxidative stability were evaluated in sonicated and nonsonicated samples. All SLs had statistically higher G′ after sonication. Sonicated LS 30, LC 30, and Blend C had a higher melting enthalpy than the nonsonicated ones, while enthalpy values in sonicated LS 20 and LC 20 samples were not statistically different than the nonsonicated ones. No significant difference between sonicated and nonsonicated samples was observed in peroxide values (1.2 ± 0.1 meq/kg, p > 0.05) and in the oxidative stability index (6.3 ± 0.2 h, p > 0.05). These results showed that HIU was effective at changing physical properties without affecting the oxidation of the samples.     

Strategies to Modulate Specialized Metabolism in Mediterranean Crops: From Molecular Aspects to Field

Plant specialized metabolites (SMs) play an important role in the interaction with the environment and are part of the plant defense response. These natural products are volatile, semi-volatile and non-volatile compounds produced from common building blocks deriving from primary metabolic pathways and rapidly evolved to allow a better adaptation of plants to environmental cues. Specialized metabolites include terpenes, flavonoids, alkaloids, glucosinolates, tannins, resins, etc. that can be used as phytochemicals, food additives, flavoring agents and pharmaceutical compounds. This review will be focused on Mediterranean crop plants as a source of SMs, with a special attention on the strategies that can be used to modulate their production, including abiotic stresses, interaction with beneficial soil microorganisms and novel genetic approaches.     

Discovery of New Antiproliferative Imidazopyrazole Acylhydrazones Able To Interact with Microtubule Systems

Even though immunotherapy has radically changed the search for anticancer therapies, there are still many different pathways that are open to intervention with traditional small molecules. To expand our investigation in the anticancer field, we report here a new series of compounds in which our previous pyrazole and imidazopyrazole scaffolds are linked to a differently decorated phenyl ring through an acylhydrazone linker. Preliminary tests on the library were performed at the National Cancer Institute (USA) against the full NCI 60 cell panel. The best compounds among the imidazopyrazole series were then tested by immunofluorescence staining for their inhibition of cell proliferation, apoptosis induction, and their effect on the cell cycle and on microtubules. Two compounds, in particular 4-benzyloxy-3-methoxybenzyliden imidazopyrazole-7-carbohydrazide showed good growth inhibition, with IC₅₀ values in the low-micromolar range, and induced apoptosis. Both compounds altered the cell-cycle phases with the appearance of polyploid cells. Immunofluorescence analysis evidenced microtubules alterations; tubulin polymerization assays and docking studies suggested the tubulin system to be the possible, although not exclusive, target of the new acylhydrazone series reported here.     

Synthesis and analysis of phase segregation of polystyrene-block-poly(methyl methacrylate) copolymer obtained by Steglich esterification from semitelechelic blocks of polystyrene and poly(methyl methacrylate)

Here, an alternative route to successfully synthesize polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) is reported. Steglich esterification was used as an effective, metal free approach for coupling carboxylic terminated PS and the hydroxyl end-functionalized PMMA chains obtained by nitroxide-mediated polymerization and atom transfer radical polymerization, respectively. α-Functionalization was obtained using 4,4′-azobis(4-cyanovaleric acid) and 2,2,2-tribromoethanol as initiators. The synthesis of PS-b-PMMA was confirmed by gel permeation chromatography and nuclear magnetic resonance (NMR), while the dependence of the diffusion coefficients of the polymers (PS, PMMA, PS/PMMA blend, and PS-b-PMMA) with their corresponding molecular weights was discussed based on the results of atomic force microscopy-based infrared spectroscopy, differential scanning calorimetry, and spectra of diffusion-ordered NMR spectroscopy. Differently from PS-b-PMMA, a partial segregation was observed for the PS/PMMA blend, affecting its thermal behavior and diffusion coefficient. The study here presented provides an easier and efficient strategy for the synthesis of PS-b-PMMA and new insights into the diffusion of polymers.     

N-methyl-2-hydroxyethylammonium oleate ionic liquid performance as corrosion inhibitor for mild steel in hydrochloric acid medium

The aim of the present study is to evaluate the performance of N-methyl-2-hydroxyethylammonium oleate ([m-2HEA][Ol]) as a corrosion inhibitor for mild steel in a 0.1-mol/L hydrochloric acid solution and also investigate the role of chloride in the inhibition mechanism. This protic ionic liquid (PIL) has formerly shown a high efficiency as a corrosion inhibitor in a neutral chloride medium. Electrochemical and weight loss measurements, surface contact angle determination, scanning electron microscopy, and Raman spectroscopy were used to understand the factors that influence the response of the studied inhibitor. Results revealed that [m-2HEA][Ol] behaves as a mixed-type adsorption inhibitor, by blocking cathodic sites and by modifying the activation energy of the anodic reaction, and it can reach up to 94–97% of inhibition efficiency. PIL adsorption was enhanced by the excess of positive charge of the mild steel. The effect of inhibitor molecule has been discussed to propose a mechanism that explains the inhibitory action of the corrosion inhibitor, pointing out the role of chloride in the inhibition mechanism.     

Retardation of Crystallization through the Addition of Dairy Phospholipids

The objective of this work was to identify the effects that milk phospholipids (PL) have on crystallization of anhydrous milk fat (AMF). Three mixtures were prepared by adding 0%, 0.01%, and 0.1% PL to AMF. Each mixture was crystallized for 90 min at 24, 26, and 28 °C. The solid fat content was measured as a function of time and fitted to the Avrami equation. Melting point, thermal behavior, viscoelastic properties, and crystal morphology were all measured at 90 min. All assays were repeated, as well as hardness, after being stored at 5 °C for 48 hours. Samples containing PL showed slower crystallization as concentration increased especially at higher temperatures (26 and 28 °C). The addition of PL caused a difference in crystal morphology resulting in visibly larger crystals at 90 min. The elasticity and hardness at 90 min were influenced by the addition of PL at 24 °C with lower values obtained in samples with PL compared to the AMF alone. No differences in hardness nor in elasticity was observed for samples crystallized at 26 and 28 °C. A decrease in melting enthalpy was observed in samples with PL indicating a reduction in crystallization at all temperatures, which was supported by crystal morphology.     

Synthesis and Biological Evaluation of Papain‐Family Cathepsin L‐Like Cysteine Protease Inhibitors Containing a 1,4‐Benzodiazepine Scaffold as Antiprotozoal Agents

Novel papain‐family cathepsin L‐like cysteine protease inhibitors endowed with antitrypanosomal and antimalarial activity were developed, through an optimization study of previously developed inhibitors. In the present work, we studied the structure–activity relationships of these derivatives, with the aim to develop new analogues with a simplified and more synthetically accessible structure and with improved antiparasitic activity. The structure of the model compounds was significantly simplified by modifying or even eliminating the side chain appended at the C3 atom of the benzodiazepine scaffold. In addition, a simple methylene spacer of appropriate length was inserted between the benzodiazepine ring and the 3‐bromoisoxazoline moiety. Several rhodesain and falcipain‐2 inhibitors displaying single‐digit micromolar or sub‐micromolar antiparasitic activity against one or both parasites were identified, with activities that were one order of magnitude more potent than the model compounds.     

Rapid and direct estimation of active biomass on granular activated carbon through adenosine tri-phosphate (ATP) determination

Granular activated carbon (GAC) filtration is used during drinking water treatment for the removal of micropollutants such as taste and odour compounds, halogenated hydrocarbons, pesticides and pharmaceuticals. In addition, the active microbial biomass established on GAC is responsible for the removal of biodegradable dissolved organic carbon compounds present in water or formed during oxidation (e.g., ozonation and chlorination) processes. In order to conduct correct kinetic evaluations of DOC removal during drinking water treatment, and to assess the state and performance of full-scale GAC filter installations, an accurate and sensitive method for active biomass determination on GAC is required. We have developed a straight-forward method based on direct measurement of the total adenosine tri-phosphate (ATP) content of a GAC sample and other support media. In this method, we have combined flow-cytometric absolute cell counting and ATP analysis to derive case-specific ATP/cell conversion values. In this study, we present the detailed standardisation of the ATP method. An uncertainty assessment has shown that heterogeneous colonisation of the GAC particles makes the largest contribution to the combined standard uncertainty of the method. The method was applied for the investigation of biofilm formation during the start-up period of a GAC pilot-scale plant treating Lake Zurich water. A rapid increase in the biomass of up to 1.1 x 10(10)cells/g GAC dry weight (DW) within the first 33 days was observed, followed by a slight decrease to an average steady-state concentration of 7.9 x 10(9)cells/g GAC DW. It was shown that the method can be used to determine the biomass attached to the GAC for both stable and developing biofilms.