Creep compliance mapping by atomic force microscopy

We present a method for mapping the spatial distribution of viscoelastic properties of heterogeneous samples using the atomic force microscope (AFM). By applying a force step load protocol to induce time dependent sample indentations we measured the local creep compliance of the sample. The creep compliance was quantified in terms of the standard linear solid model to give maps of the instant glassy modulus, the equilibrium rubbery modulus, and the retardation time. To reduce the influence of plastic deformations, the sample was preformed with an initial preload step. Different polymer samples with a homogeneous or a heterogeneous material composition on a microscopic scale were investigated.     

Enantioselective Titanium‐Catalyzed Cyanation Reactions of Carbonyl Compounds

This review surveys the recent developments in enantioselective titanium‐catalyzed cyanation reactions of carbonyl compounds, covering the literature since the beginning of 2008. It well demonstrates that this reaction constitutes an important tool in organic synthesis, still attracting a considerable interest due to the potential use of enantiopure cyanohydrins as natural products and useful synthetic intermediates in the synthesis of biologically active molecules. Abbreviations: Ac: acetyl; Ar: aryl; BINOL: 1,1′‐bi‐2‐naphthol; BINOLAM: bis(diethylaminomethyl)‐1,1‘‐binaphthol; Bn: benzyl; Cy: cyclohexyl; DFT: density functional theory; DMAP: 4‐(dimethylamino)pyridine; ee: enantiomeric excess; Naph: naphthyl; r.t.: room temperature; salen: 1,2‐bis(salicylidenamino)ethane; TADDOL: α,α,α′,α′‐tetraphenyl‐2,2‐dimethyl‐1,3‐dioxolane‐4,5‐dimethanol; TEA: trimethylamine; THF: tetrahydrofuran; TMS: trimethylsilyl; Tol: tolyl.

     

Modeling of Rhamnolipid Biosurfactant Production: Estimation of Kinetic Parameters by Genetic Algorithm

Studies about kinetics and modeling of production parameters for biosurfactants are essential to the development of efficient processes from an economic point of view. In this sense, this work evaluated the performance of four nonstructured models to explain the experimental data for biomass growth, substrate consumption, and rhamnolipid production using glycerol as carbon source and a Pseudomonas aeruginosa strain. The kinetic parameters of each model were estimated using a global search method known as genetic algorithm and numerical discretization of differential equations by the Runge–Kutta 4th order method. The main result of this study showed that the Monod model best represented the experimental data, with μ_max values of 0.06 h⁻¹, K_S of 50.8 g L⁻¹, Y_X/S of 0.43 g g⁻¹, and Y_P/X equal to 0.017 g g⁻¹.     

Synthesis and Anticancer Properties of Oxazepines Related to Azaisoerianin and IsoCoQuines

In this article, we report the synthesis and biological properties of a series of novel oxazepines related to isoCA-4 having significant antitumor properties. Among them, three oxazepin-9-ol derivatives display a nanomolar or a sub-nanomolar cytotoxicity level against five human cancer cell lines (HCT116, U87, A549, MCF7, and K562). It was demonstrated that the lead compound in this series inhibits tubulin assembly with an IC₅₀ value of 1 μM and totally arrests the cellular cycle in the G2/M phase at the low concentration of 5 nM in HCT116 and K562 cells. Molecular modeling studies perfectly corroborates these promising results.     

pH- and heat-induced structural changes of bovine α-lactalbumin in response to oleic acid binding

Bovine α-lactalbumin (α-LA) is able to interact with fatty acids, resulting in structural changes that are potentially responsible for the HAMLET/BAMLET role. Different states of α-LA induced by pH, temperature and fatty acid binding have been examined. Evidences of the structural changes of α-LA in molten globule and native states in correlation with oleic acid (OA) binding are shown using fluorescence spectroscopy and in silico approach. In addition, the α-LA was subjected to automated docking analysis, to better understand the interaction with oleic acid, using the PatchDock algorithm. The experimental results demonstrate a more flexible conformation of the protein at pH 2.5 when compared to neutral pH, thus facilitating the oleic acid binding to α-LA. The quenching experiments indicate the remarkable increase in the content of molten globule state at pH 2.5 and a more compact and rigid structure for α-LA–OA complexes at pH 7.0. The docking results are consistent with the experimental data concerning the thermal stability of the α-LA–OA complex. α-LA in different conformations/complexes was sensitive to pH and temperature. Several different molecular species induced by pH, heat treatment and oleic acid binding were suggested. The structure of the protein was more flexible at acidic pH, therefore favoring the hydrophobic exposure.     

Extrusion of Rice,Bean and Corn Starches: Extrudate Structure and Molecular Changes in Amylose and Amylopectin

The objective of this study was to evaluate the effects of starch source and amylose content on the expansion ratio, density, and texture of expanded extrudates, as well as to investigate the structural and molecular changes that occur in starch granules as a function of extrusion. The starches employed were rice starches (8%, 20%, and 32% amylose), carioca bean starch (35% amylose), and Hylon V^® corn starch (55% amylose). The extrudates from rice starches containing 20% and 32% amylose exhibited the highest expansion ratio, while, extrudates from Hylon V^® corn starch containing 55% amylose exhibited the lowest expansion ratio. The hardness values of the extrudates with 55% amylose were twice those of the extrudates with 20%, 32%, and 35% amylose. An additional finding was that although the amylopectin promoted the expansion of the gelatinized starch matrix, it failed to strengthen and sustain the walls of the extrudate bubbles during expansion.     

Multivariate Optimization for the Development of a Fast and Simple Ultrasound-Assisted Extraction Procedure for Multielemental Determination in Tea Leaves by Inductively Coupled Plasma Optical Emission Spectrometry (ICP OES)

The current study describes a fast and efficient procedure of ultrasound-assisted extraction for determination of Ca, Mg, K, Na, Cu, Zn, Mn, and Al in tea leaves by inductively coupled plasma optical emission spectrometry (ICP OES). The variables of procedure were optimized using the Box–Behnken design and the conditions selected were nitric acid concentration (1.0 mol L^?1), sonication time (7 min), and sonication temperature (75 °C). The extraction efficiency was calculated using the analyte concentration obtained by a total digestion procedure as reference. Accuracy was confirmed by analysis of certified reference material of apple leaves (NIST 1515) and spinach leaves (NIST 1570a) using the procedure proposed. A statistical evaluation using Student’s t test showed that there is no significant difference between the value obtained with the proposed procedure and the certified value, at 95% confidence level. The proposed procedure was successfully applied and is a good alternative to conventional acid digestion procedure and can be applied to routine analysis for determination of Ca, Mg, K, Na, Zn, Mn, Cu, and Al in tea leaves used for the preparation of infusions.     

Lipid Oxidation in Oil‐in‐Water Emulsions: Involvement of the Interfacial Layer

More polyunsaturated fats in processed foods and fewer additives are a huge demand of public health agencies and consumers. Consequently, although foods have an enhanced tendency to oxidize, the usage of antioxidants, especially synthetic antioxidants, is restrained. An alternate solution is to better control the localization of reactants inside the food matrix to limit oxidation. This review establishes the state‐of‐the‐art on lipid oxidation in oil‐in‐water (O/W) emulsions, with an emphasis on the role of the interfacial region, a critical area in the system in that respect. We first provide a summary on the essential basic knowledge regarding (i) the structure of O/W emulsions and interfaces and (ii) the general mechanisms of lipid oxidation. Then, we discuss the factors involved in the development of lipid oxidation in O/W emulsions with a special focus on the role played by the interfacial region. The multiple effects that can be attributed to emulsifiers according to their chemical structure and their location, and the interrelationships between the parameters that define the physicochemistry and structure of emulsions are highlighted. This work sheds new light on the interpretation of reported results that are sometimes ambiguous or contradictory.