Synthesis and experimental/computational characterization of sorghum procyanidins-gelatin nanoparticles.

In this research, sorghum procyanidins (PCs) and procyanidin B1 (PB1) were encapsulated in gelatin (Gel) to form nanoparticles as a strategy to maintain their stability and bioactivity and for possible applications as inhibitors of metalloproteinases (MMPs) of the gelatinase type. Encapsulation was carried out by adding either PCs or PB1 to an aqueous solution of A- or B-type Gel (GelA or GelB) at different concentrations and pH. Under this procedure, the nanoparticles PCs-GelA, PCs-GelB, PB1-GelA, and PB1-GelB were synthesized and subsequently characterized by experimental and computational methods. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) revealed that all types of nanoparticles had sizes in the range of 22-138 nm and tended to adopt an approximately spherical morphology with a smooth surface, and they were immersed in a Gel matrix. Spectral analysis indicated that the nanoparticles were synthesized by establishing hydrogen bonds and hydrophobic interactions betweenGel and the PCs or PB1. Study of simulated gastrointestinal digestion suggested that PCs were not released from the Gel nanoparticles, and they maintained their morphology (SEM analysis) and antioxidant activity determined by Trolox-equivalent antioxidant capacity (TEAC) assay. Computational characterization carried out through molecular docking studies of PB1 with Gel or (pro-)metalloproteinase-2 [(pro-)MMP-2], as a model representative of the PCs, showed very favorable binding energies (around -5.0 kcal/mol) provided by hydrogen bonds, van der Waals interactions, and desolvation. Additionally, it was found that PB1 could act as a selective inhibitor of (pro-)MMP-2.

Theoretical Prediction of Structures, Vibrational Circular Dichroism, and Infrared Spectra of Chiral Be4B8 Cluster at Different Temperatures.

Lowest-energy structures, the distribution of isomers, and their molecular properties depend significantly on geometry and temperature. Total energy computations using DFT methodology are typically carried out at a temperature of zero K; thereby, entropic contributions to the total energy are neglected, even though functional materials work at finite temperatures. In the present study, the probability of the occurrence of one particular Be4B8 isomer at temperature T is estimated by employing Gibbs free energy computed within the framework of quantum statistical mechanics and nanothermodynamics. To identify a list of all possible low-energy chiral and achiral structures, an exhaustive and efficient exploration of the potential/free energy surfaces is carried out using a multi-level multistep global genetic algorithm search coupled with DFT. In addition, we discuss the energetic ordering of structures computed at the DFT level against single-point energy calculations at the CCSD(T) level of theory. The total VCD/IR spectra as a function of temperature are computed using each isomer's probability of occurrence in a Boltzmann-weighted superposition of each isomer's spectrum. Additionally, we present chemical bonding analysis using the adaptive natural density partitioning method in the chiral putative global minimum. The transition state structures and the enantiomer-enantiomer and enantiomer-achiral activation energies as a function of temperature evidence that a change from an endergonic to an exergonic type of reaction occurs at a temperature of 739 K.

Relative Populations and IR Spectra of Cu38 Cluster at Finite Temperature Based on DFT and Statistical Thermodynamics Calculations.

The relative populations of Cu38 isomers depend to a great extent on the temperature. Density functional theory and nanothermodynamics can be combined to compute the geometrical optimization of isomers and their spectroscopic properties in an approximate manner. In this article, we investigate entropy-driven isomer distributions of Cu38 clusters and the effect of temperature on their IR spectra. An extensive, systematic global search is performed on the potential and free energy surfaces of Cu38 using a two-stage strategy to identify the lowest-energy structure and its low-energy neighbors. The effects of temperature on the populations and IR spectra are considered via Boltzmann factors. The computed IR spectrum of each isomer is multiplied by its corresponding Boltzmann weight at finite temperature. Then, they are summed together to produce a final temperature-dependent, Boltzmann-weighted spectrum. Our results show that the disordered structure dominates at high temperatures and the overall Boltzmann-weighted spectrum is composed of a mixture of spectra from several individual isomers.

Chemical composition and antioxidant-prooxidant potential of a polyphenolic extract and a proanthocyanidin-rich fraction of apple skin.

The apple is a food rich in diverse classes of polyphenols (PP), among which the proanthocyanidins (PCs), which are primarily concentrated in the skin, are one of the most abundant. These compounds are of considerable interest for their possible positive health effects because of their antioxidant properties. However, depending on the classes of PP present (chemical composition) and their relative concentrations in the apple skin, their antioxidant effects vary and some of their components can even generate prooxidant effects. This work determined the chemical composition and antioxidant-prooxidant potential of a polyphenolic extract (PPE) and a proanthocyanidin-rich fraction (PRF) of apple skin, along with the contribution of their most abundant individual compounds, based on their copper chelating ability, ease in reducing peroxidase-generated free radicals and TEAC (Trolox-Equivalent Antioxidant Capacity) assay. For this purpose, chromatographic and colorimetric methods were used. The majority compounds identified in PPE were flavan-3-ols (44.58%), flavonols (42.89%) and dihydrochalcones (11.60%). In PRF, we detected monomers and oligomers from dimers to heptamers, which were composed of 97% (-)-epicatechin and 3% (+)-catechin. The antioxidant potential was notably higher in PRF than in PPE. The (-)-epicatechin monomer and the procyanidin B2 dimer showed more ease in reducing peroxidase-generated free radicals compared to other compounds of the apple skin, whereas phloridzin dihydrochalcone produced prooxidant effects.

Development of an antioxidant biomaterial by promoting the deglycosylation of rutin to isoquercetin and quercetin.

Quercetin-3-O-rutinoside (rutin), quercetin-3-O-glucoside (isoquercetin) and quercetin have shown antioxidant, cytoprotective, vasoprotective, antiproliferative and antiinflammatory properties. The aim of this work was to determine the conversion of rutin to isoquercetin and quercetin during the production of poly(l-lactic acid) films with potential to deliver these flavonoids toward tissues, pharmaceuticals or food matrices. Three poly(l-lactic acid) formulations with 17.7, 39.6 and 39.1mg/g of rutin were prepared by the extrusion process. Processing temperatures (130-165°C) promoted the deglycosylation of rutin to produce isoquercetin and subsequently quercetin, identified by high performance liquid chromatography coupled to mass spectrometry. The effect of the process on the antioxidant activity of the films was determined by measuring the capacity to scavenge 2,2 diphenyl-1-picrylhydrazyl radicals. The material with the highest proportion of quercetin showed the highest antioxidant activity which could be used to produce delivering devices of the flavonoids to tissues, pharmaceuticals or food matrices.

Computational study of the structure-free radical scavenging relationship of procyanidins.

Procyanidins (PCs) are effective free radical scavengers, however, their antioxidant ability is variable because they have different degrees of polymerisation, are composed by distinct types of subunits and are very susceptible to changes in conformation. In this work the structure-free radical scavenging relationship of monomers, dimers and trimers of PCs was studied through the hydrogen atom transfer (HAT), sequential proton-loss electron-transfer (SPLET) and single electron transfer followed by proton transfer (SET-PT) mechanisms in aqueous phase, employing the Density Functional Theory (DFT) computational method. The structure-free radical scavenging relationship of PCs showed a very similar behaviour in HAT and SET-PT mechanisms, but very different in the SPLET mechanism. The structural factor that showed more effects on the ability of PCs to scavenge free radicals in aqueous phase was the conformation.

Propiedades y posibles aplicaciones de las proteínas de salvado de trigo / Properties and application possibilities of wheat bran proteins

Resumen El salvado de trigo se destina principalmente al consumo animal, por lo que algunos de sus componentes son subutilizados, representando oportunidades de valor agregado. Constituye las capas externas del grano y contiene hasta 18 % en peso de proteínas con mejor calidad que las de la harina. Estas proteínas no son aprovechadas debido a que la mayoría están protegidas por una matriz de polisacáridos, indigerible para el sistema gastrointestinal humano, por lo que es necesaria su extracción. Tradicionalmente, las proteínas de salvado han sido recuperadas mediante extracción alcalina y se han propuesto como ingredientes para la elaboración de productos alimenticios. Sin embargo, su uso es casi inexistente, debido a que los procesos de extracción son agresivos y no redituables. El objetivo del presente trabajo fue describir las propiedades de las proteínas del salvado de trigo, así como sus usos potenciales. Entre sus propiedades destacan la digestibilidad, el perfil de aminoácidos y la capacidad de absorción de grasa. La fracción soluble en agua de estas proteínas, por su fácil extracción, podría tener valor agregado al utilizarse en tecnologías emergentes: como fuente de péptidos bioactivos, en la producción de nanopartículas con aplicaciones industriales o como matrices para procesos de biomineralización artificial.

Abstract Wheat bran is mainly intended for animal consumption and some of its components are underutilized, representing value-added opportunities. It forms the outer layers of the grain and contains up to 18 % by weight of proteins of better quality than those of flour. These proteins are not exploited because most are protected by a matrix of polysaccharides, which is indigestible by the human gastrointestinal system" so their extraction is necessary. Traditionally, wheat bran proteins have been recovered by alkaline extraction and have been proposed as ingredients for the manufacture of foodstuffs. However, their use is almost non-existent because the extraction processes are aggressive and not profitable. The aim of the present review is to present the proper ties of wheat bran proteins, as well as, their potential uses. Among their properties, the digestibility, lipid absorption capacity and aminoàcid pattern are highlighted. The water soluble fraction of these proteins, because of their easy extraction, could have an added value from the perspetive of emerging technologies, for example, as a source of bioactive peptides, in the production of nanoparticles with industrial applications or as matrices for artificial biomineralization processes.

Spectroscopic and computational study of the major oxidation products formed during the reaction of two quercetin conformers with a free radical.

The goal of this research was to determine whether there are differences between the major oxidation products formed during the reaction of quercetin unhydrate (QUH) or quercetin dihydrate (QDH) with the 2,2-diphenyl-1-picrylhydrazyl free radical (DPPH), as well as to identify some properties of these products. The study was carried out employing spectroscopic and computational methods, in order to know the effect of different conformations of quercetin on the mechanism of free radical scavenging. The results demonstrated that although the same oxidation products may be formed from QUH and QDH, their properties and the predominant product were different in each. The o-quinone was the predominant oxidation product of QUH, whereas in QDH it was established an equilibrium between o-quinone and extended p-quinone.

Nanotubus de carbono y bionanotecnología / Carbon nanotubes and bionanotechnology

Los nanotubos de carbono (NTC) son estructuras artificiales novedosas que presentan propiedades físicas inusuales. Estas propiedades han hecho a los NTC objeto de una gran cantidad de estudios, los cuales han revelado un inmenso potencial de aplicación en diferentes áreas, tales como la electrónica, la física y la biología. En este trabajo se revisan los conceptos básicos sobre la química, obtención y modificación de los NTC, y se discute su posible utilización en sistemas biológicos.