Valentin I. Popa

A critical review of methods for characterisation of polyphenolic compounds in fruits and vegetables

Phenolic compounds, ubiquitous in plants, are of considerable interest and have received more and more attention in recent years due to their bioactive functions. Polyphenols are amongst the most desirable phytochemicals due to their antioxidant activity. These components are known as secondary plant metabolites and possess also antimicrobial, antiviral and anti-inflammatory properties along with their high antioxidant capacity. Many efforts have been made to provide a highly sensitive and selective analytical method for the determination and characterisation of polyphenols. The aim of this paper is to provide information on the most recent developments in the chemical investigation of polyphenols emphasising the extraction, separation and analysis of these compounds by chromatographic and spectral techniques.

Thermal stability, antioxidant activity, and photo-oxidation of natural polyphenols

The thermal stability (60°C, 80°C, 100°C), antioxidant activity, and ultraviolet C light (UV-C) stability of standard polyphenols solutions (catechin, gallic acid, and vanillic acid) and of vegetal extracts from spruce bark and grape seeds were investigated. Exposure of the standard solutions and vegetal extracts to high temperatures revealed that phenolic compounds were also relatively stable (degradations ranged from 15 % to 30 % after 4 h of exposure). The highest antioxidant activity was obtained for ascorbic acid and gallic acid followed by catechin and caffeic acid and the grape seeds. The results show that, after 3 h of UV-C exposure, approximately 40 % of vanillic acid, 50 % of gallic acid, and 83 % of catechin were removed. Similar degradation rates were observed for vegetal extracts, with the exception of the degradation of catechin (40 %) from grape seeds. In addition, the photo-oxidation of polyphenols in the presence of food constituents such as citric acid, ascorbic acid, sodium chloride, and sodium nitrate was assessed.

Optimization of ultrasound-assisted extraction of polyphenols from spruce wood bark.

Here we describe the ultrasound-assisted extraction of the phenolic compounds from spruce wood bark and present a straight-forward experimental planning method, allowing the optimisation of the process. The effect of ethanol concentration, temperature and extraction time were evaluated through a 3(2)·2 experimental planning. The efficiency of the extraction process was appreciated based on factorial ANOVA results. The maximum extraction yield of total polyphenols (13.232mg gallic acid equivalents (GAE)/g of spruce bark tested) was obtained using a process time of 60min, an extraction temperature of 54°C and a concentration of ethanol of 70% respectively. These results indicate that an important quantity of bioactive compounds can be extracted from spruce wood bark by ultrasound assisted extraction technology.

Chapter 13 – Hemicelluloses: Major Sources, Properties and Applications

Publisher Summary This chapter deals with the major representatives of hemicelluloses, their properties, and application. Hemicelluloses are plant cell wall polysaccharides that are not soluble in water, but they can be separated by aqueous alkali, or hydrolyzed by diluted acids. The main hemicelluloses include the following polysaccharides: xylan, glucuronoxylan, arabinoxylan, mannan, glucomannan, and galactoglucomannan, and their representatives are different as a function of the plant species. The general structure of hemicelluloses is based on a sugar backbone substituted with side chains. The nature of the monosaccharide, as well as the linkages between structural units, determines some properties, such as solubility and the three-dimensional conformation of hemicelluloses. At present, there is an increasing interest to develop new applications of hemicelluloses as raw materials for chemical industry and also in the fields of food and pharmaceutical industries.

A Comparative Analysis of the ‘Green’ Techniques Applied for Polyphenols Extraction from Bioresources

From all the valuable biomass extractives, polyphenols are a widespread group of secondary metabolites found in all plants, representing the most desirable phytochemicals due to their potential to be used as additives in food industry, cosmetics, medicine, and others fields. At present, there is an increased interest to recover them from plant of spontaneous flora, cultivated plant, and wastes resulted in agricultural and food industry. That is why many efforts have been made to provide a highly sensitive, efficiently, and eco‐friendly methods, for the extraction of polyphenols, according to the green chemistry and sustainable development concepts. Many extraction procedures are known with advantages and disadvantages. From these reasons, the aim of this article is to provide a comparative analysis regarding technical and economical aspects related to the most innovative extraction techniques studied in the last time: microwave‐assisted extraction (MAE), supercritical fluid extraction (SFE), and ultrasound‐assisted extraction (UAE).

Kinetic modeling of the ultrasound-assisted extraction of polyphenols from Picea abies bark.

In this paper, the kinetics of polyphenols extraction from spruce bark (Picea abies) under ultrasounds action was investigated. Studies were performed in order to express the effect of some specific parameters (as: ultrasounds, surface contact between solvent and solid, extraction time and temperature) on the total phenolic content (TPC). Experiments were performed in the presence and absence of ultrasounds, using different contact surfaces between solvent and solid, for times from 5 to 75min and temperatures of 318, 323 and 333K. All these factors have a positive influence on the process, enhancing the extraction rate by recovering higher amounts of polyphenols. The process takes place in two stages: a fast one in the first 20-30min (first stage), followed by a slow one approaching to an equilibrium concentration after 40min (second stage). In these conditions, the second-order kinetic model was successfully developed for describing the mechanism of ultrasound-assisted extraction of polyphenols from P. abies bark. Based on this model, values of second-order extraction rate constant (k), initial extraction rate (h), saturation concentration (Cs) and activation energy (Ea) could be predicted. Model validation was done by plotting experimental and predicted values of TPCs, revealing a very good correlation between the obtained data (R(2)>0.98).

Advances Concerning Lignin Utilization in New Materials

After cellulose, lignin represents the second main component of vegetal biomass. The estimation of lignin produced annually through biosynthesis indicates a quantity of 2x1010 tons.

Seasonal variations of the phenolic constituents in bilberry (Vaccinium myrtillus L.) leaves, stems and fruits, and their antioxidant activity.

The seasonal variations of the content and diversity of phenolic compounds, as well as the antioxidant activity of leaves, stems and fruits of bilberry collected in May, July and September, were evaluated for two consecutive years. UPLC/MS(n) analyses showed the predominance of anthocyanins in fruits, caffeic acid derivatives in leaves whereas flavanol oligomers represented more than half of the phenolic compounds in stems. Thioacidolysis revealed degrees of polymerization between 2 and 4 and (-)-epicatechin as the main flavanol unit. The sum of the phenolic compounds by UPLC was highly correlated with the total polyphenol content and the antioxidant activity in the DPPH test for all the extracts except for May leaves. The latter were relatively rich in p-coumaric acid derivatives. Seasonal effects were more marked for leaves, which exhibited higher antioxidant activities and phenolic contents in July and September when these parameters were at their highest in July for stems.

Changes of supramolecular cellulose structure and accessibility induced by the processive endoglucanase Cel9B from Paenibacillus barcinonensis

Abstract A newly identified cellulase with a high polysaccharide degrading potential and a processive mode of action, has been evaluated on cellulose fibers. Cellulase Cel9B from Paenibacillus barcinonensis is a modular endoglucanase with the domain structure GH9-CBM3c-Fn3-CBM3b, consisting of a family nine catalytic module GH9, an auxiliary module CBM3c, a fibronectin-like module Fn3, and a functional cellulose binding module CBM3b. The whole cellulase Cel9B (E1) and two truncated forms of the enzyme that consist of the catalytic module linked to the auxiliary module, GH9-CBM3c (E2), and of the cellulose binding module of the enzyme, CBM3b (CBD), were applied to softwood dissolving pulp. The changes in the supramolecular structure and morphology of the fibres after the enzymatic treatment were evaluated by viscosimetry, X-ray diffraction (XRD), thermogravimetric analysis, differential scanning calorimetry and scanning electron microscopy (SEM). XRD studies provided the crystallite size, interplanar distances and crystallinity index of the samples before and after the enzymatic treatment. The treatment with cellulases E1 and E2 decreased the degree of polymerization and increased the crystallinity index of the pulp. Both E1 and E2 had a pronounced capacity for removing fuzz and improved the smoothness and surface appearance of the fibers, as shown by SEM. On the other hand, CBD proved to be less effective under the tested conditions. Moreover, the solubility of dissolving pulp in alkaline solutions has been evaluated as an indirect measure of cellulose accessibility. A notable enhancement in alkaline solubility of the samples treated with the cellulases was observed.

Lignins and Polyphenols in Bioremediation

Bioremediation by definition is concerned with the fate and, if necessary, removal of unwanted organic chemicals from soil and/or water. At present, bioremediation is considered as a less expensive alternative to physical and chemical means of degradation of organic pollutants. It deals with substances that are anthropogenic, distributed in nature and recalcitrant. At the same time, it is not lacked of interest to involve the bioremediation to improve some properties of the soils. The lignins are biosynthesized in plants to carry out different functions, such as storage of energy, bonding agent between plant cells, protection agent against microorganisms, antioxidant, and hydrophobic agent. Lignin is an important precursor for stabilized soil organic carbon. Terrestrial ecosystems that produce large amounts of lignin are thought to have high potential for sequestering carbon which can decrease global warming by reducing atmospheric CO2. After the death of the plants, their compounds are transformed at the soil level with humus formation. Based on biological transformation some utilization of lignins could be developed among other things such as crop cultivation and bioremediation (Abaecherli and Popa, 2005).