Structure and Oligomers Distribution of Commercial Tara (Caesalpina spinosa) Hydrolysable Tannin

Solvent extracted commercial Tara tanninextract have been examined by Matrix Assisted LaserDesorption/Ionisation Time-of-Flight (MALDI-TOF)mass spectrometry and by High Pressure LiquidChromatography (HPLC). The Tara extract has beenfound to be composed of a series of oligomers ofpolygallic acid attached by an ester link to one quinicacid. They constitute the oligomers in higherproportion in the extract. Other polygallic chains linkedto one only or two repeating units such as caffeic acidand methylated quinic, methylated gallic andmethylated caffeic acids are also present. Negativeion mode MALDI-TOF showed that somecarbohydrate residues appear to still be present,linked to the polyphenolic material of the extract buttheir proportion is very low as would be expected of asolvent extracted tannin

Modification and stabilization of the reactivity of tannins chemically treated : the applications to adhesive resins and eco-sustainable foams preparation

L'objectif de ce travail de thèse a été de produire des matériaux expansés à partir de produits d'origine naturelle, en particulier à partir de tanins. Au moment où cette thèse a débuté, des études étaient publiées sur la possibilité d'élaborer ce type de matériaux avec des formulations qui comportaient du formaldéhyde. Cela allait à l'encontre du caractère naturel recherché puisqu'en fait, on utilisait des produits naturels et les faisait réagir avec un produit cancérogène. Il n'était donc pas possible de les présenter comme des matériaux « verts ». Aussi, nous avons voulu au cours de ce travail, élaborer des matériaux expansés uniquement à partir de produits naturels ou en découlant. Les tanins sont des substances naturelles chimiquement actives qui peuvent être utilisées afin de remplacer des produits homologues dérivés du pétrole comme le phénol par exemple qui présente des caractéristiques de réactivité chimique très similaires à celles des tanins condensés. Des formulations comportant des tanins condensés ont d'ailleurs déjà été étudiées pour élaborer des matériaux expansés. En considérant cela, ce travail de thèse s'est déroulé sous la forme de différents projets convergents vers un objectif commun: la production de mousses aux tanins plus naturelles et plus intéressantes pour l'industrie. Cinq projets ont ainsi été menés : 1. analyses de différents tanins, condensés, hydrolysables et synthétiques ; 2. production de mousses aux tanins sans utilisation de formaldéhyde ; 3. production de mousses aux tanins sans solvants ; 4. production de mousses aux tanins rigides ou élastiques ; 5. production de mousses aux tanins, sans acides, mais avec une catalyse alcalineThe aim of this thesis was to produce foamed materials from natural products, especially from tannins. At the time this thesis began, studies were published on the possibility of doing this type of materials with formaldehyde containing formulations. This was contrary to the desired natural character because in fact, were used natural products reacted with carcinogenic product. It was not possible to present them as "green" materials. During this thesis our aim was to develop expanded materials only from natural or bio-derived raw materials. Tannins are chemically active natural substances that can be used to replace homologous oil derivatives such as phenol which has characteristics of chemical reactivity very similar to those of condensed tannins. Formulations containing condensed tannins have already been studied to develop expanded materials. Considering this argument, this thesis takes place in the form of various projects converging towards a common goal: production of foams with more natural impact and interesting for tannins industry. Five projects have been completed: 1. analysis of various tannins, condensed, hydrolysable and synthetic ; 2. tannin foams production without the use of formaldehyde ; 3. tannin foams production without solvents ; 4. tannin foams production with rigid or elastic behavior ; 5. tannin foams production without acids, but with an alkaline catalysi

Modification et stabilisation de la réactivité de tanins traités chimiquement : applications à la préparation de résines adhésives et de mousses écosoutenables

The aim of this thesis was to produce foamed materials from natural products, especially from tannins. At the time this thesis began, studies were published on the possibility of doing this type of materials with formaldehyde containing formulations. This was contrary to the desired natural character because in fact, were used natural products reacted with carcinogenic product. It was not possible to present them as "green" materials. During this thesis our aim was to develop expanded materials only from natural or bio-derived raw materials. Tannins are chemically active natural substances that can be used to replace homologous oil derivatives such as phenol which has characteristics of chemical reactivity very similar to those of condensed tannins. Formulations containing condensed tannins have already been studied to develop expanded materials. Considering this argument, this thesis takes place in the form of various projects converging towards a common goal: production of foams with more natural impact and interesting for tannins industry. Five projects have been completed: 1. analysis of various tannins, condensed, hydrolysable and synthetic ; 2. tannin foams production without the use of formaldehyde ; 3. tannin foams production without solvents ; 4. tannin foams production with rigid or elastic behavior ; 5. tannin foams production without acids, but with an alkaline catalysisL'objectif de ce travail de thèse a été de produire des matériaux expansés à partir de produits d'origine naturelle, en particulier à partir de tanins. Au moment où cette thèse a débuté, des études étaient publiées sur la possibilité d'élaborer ce type de matériaux avec des formulations qui comportaient du formaldéhyde. Cela allait à l'encontre du caractère naturel recherché puisqu'en fait, on utilisait des produits naturels et les faisait réagir avec un produit cancérogène. Il n'était donc pas possible de les présenter comme des matériaux « verts ». Aussi, nous avons voulu au cours de ce travail, élaborer des matériaux expansés uniquement à partir de produits naturels ou en découlant. Les tanins sont des substances naturelles chimiquement actives qui peuvent être utilisées afin de remplacer des produits homologues dérivés du pétrole comme le phénol par exemple qui présente des caractéristiques de réactivité chimique très similaires à celles des tanins condensés. Des formulations comportant des tanins condensés ont d'ailleurs déjà été étudiées pour élaborer des matériaux expansés. En considérant cela, ce travail de thèse s'est déroulé sous la forme de différents projets convergents vers un objectif commun: la production de mousses aux tanins plus naturelles et plus intéressantes pour l'industrie. Cinq projets ont ainsi été menés : 1. analyses de différents tanins, condensés, hydrolysables et synthétiques ; 2. production de mousses aux tanins sans utilisation de formaldéhyde ; 3. production de mousses aux tanins sans solvants ; 4. production de mousses aux tanins rigides ou élastiques ; 5. production de mousses aux tanins, sans acides, mais avec une catalyse alcalin

Modification et stabilisation de la réactivité de tanins traités chimiquement : applications à la préparation de résines adhésives et de mousses écosoutenables

The aim of this thesis was to produce foamed materials from natural products, especially from tannins. At the time this thesis began, studies were published on the possibility of doing this type of materials with formaldehyde containing formulations. This was contrary to the desired natural character because in fact, were used natural products reacted with carcinogenic product. It was not possible to present them as "green" materials. During this thesis our aim was to develop expanded materials only from natural or bio-derived raw materials. Tannins are chemically active natural substances that can be used to replace homologous oil derivatives such as phenol which has characteristics of chemical reactivity very similar to those of condensed tannins. Formulations containing condensed tannins have already been studied to develop expanded materials. Considering this argument, this thesis takes place in the form of various projects converging towards a common goal: production of foams with more natural impact and interesting for tannins industry. Five projects have been completed: 1. analysis of various tannins, condensed, hydrolysable and synthetic ; 2. tannin foams production without the use of formaldehyde ; 3. tannin foams production without solvents ; 4. tannin foams production with rigid or elastic behavior ; 5. tannin foams production without acids, but with an alkaline catalysisL'objectif de ce travail de thèse a été de produire des matériaux expansés à partir de produits d'origine naturelle, en particulier à partir de tanins. Au moment où cette thèse a débuté, des études étaient publiées sur la possibilité d'élaborer ce type de matériaux avec des formulations qui comportaient du formaldéhyde. Cela allait à l'encontre du caractère naturel recherché puisqu'en fait, on utilisait des produits naturels et les faisait réagir avec un produit cancérogène. Il n'était donc pas possible de les présenter comme des matériaux « verts ». Aussi, nous avons voulu au cours de ce travail, élaborer des matériaux expansés uniquement à partir de produits naturels ou en découlant. Les tanins sont des substances naturelles chimiquement actives qui peuvent être utilisées afin de remplacer des produits homologues dérivés du pétrole comme le phénol par exemple qui présente des caractéristiques de réactivité chimique très similaires à celles des tanins condensés. Des formulations comportant des tanins condensés ont d'ailleurs déjà été étudiées pour élaborer des matériaux expansés. En considérant cela, ce travail de thèse s'est déroulé sous la forme de différents projets convergents vers un objectif commun: la production de mousses aux tanins plus naturelles et plus intéressantes pour l'industrie. Cinq projets ont ainsi été menés : 1. analyses de différents tanins, condensés, hydrolysables et synthétiques ; 2. production de mousses aux tanins sans utilisation de formaldéhyde ; 3. production de mousses aux tanins sans solvants ; 4. production de mousses aux tanins rigides ou élastiques ; 5. production de mousses aux tanins, sans acides, mais avec une catalyse alcalin

Antibacterial activity of tannins towards Pseudomonas syringae pv. tomato, and their potential as biostimulants on tomato plants

Pseudomonas syringae pv. tomato (Pst), the causal agent of bacterial speck of tomato, is a significant cause of economic losses in tomato crops. This disease is mainly controlled with preventive use of cupric salt formulations. Antibacterial activity of the tannins U1, U2, U3 and U4, applied alone at 1% w/v concentration or in combination with half (0.045% w/v) of standard of copper hydroxide treatments, was assayed for effects on Pst. In vitro, the four tannins completely inhibited Pst colony formation after 24 h, but U2 (quebracho tannins) +1/2 Cu(OH)2 allowed Pst growth after 48 h of incubation, indicating that, since U2 is composed of high molecular condensed tannins it is likely that their structures have chelated the copper hydroxide much more then hydrolysable ones, thus inactivating copper hydroxide and tannins. In fact, this activity of the tannins was equivalent to that for 0.045% w/v of copper hydroxide. Effects of tannins on tomato plant growth were also assessed. On seedlings, long-term U1 treatments increased dry weight of shoots compared to copper hydroxide, but not to water treatment. The U4 treatment increased the NBI values compared to copper treatment but did not show significant differences compared to the water treatment. Inhibitory activity of tannin treatments reduced disease by 37-62%, and 60% after copper treatment, while disease severity was reduced by 33-54% after treating plants with tannins and 36% after copper treatment. On mature plants treated once, the disease reduction was 27-39% after tannin treatments and 44% after copper treatment, while severity was reduced by 50-60% from tannin treatments, and 47% by copper. In seedlings and mature plants, these reductions were similar (P > 0.05) for the tannins and copper treatments. This study indicates a novel crop protection strategy using natural products as alternatives to xenobiotic compounds

Tannin Extraction from Chestnut Wood Waste: From Lab Scale to Semi-Industrial Plant

The chestnut tree (Castanea sativa, Mill.) is a widespread plant in Europe whose fruits and wood has a relevant economic impact. Chestnut wood (CW) is rich in high-value compounds that exhibit various biological activities, such as antioxidant as well as anticarcinogenic and antimicrobial properties. These metabolites can be mainly divided into monomeric polyphenols and tannins. In this piece of work, we investigated a sustainable protocol to isolate enriched fractions of the above-mentioned compounds from CW residues. Specifically, a sequential extraction protocol, using subcritical water, was used as a pre-fractionation step, recovering approximately 88% of tannins and 40% of monomeric polyphenols in the first and second steps, respectively. The optimized protocol was also tested at pre-industrial levels, treating up to 13.5 kg CW and 160 L of solution with encouraging results. Ultra- and nanofiltrations were used to further enrich the recovered fractions, achieving more than 98% of the tannin content in the heavy fraction, whilst the removed permeate achieved up to 752.71 mg GAE/gext after the concentration (75.3%). Samples were characterized by means of total phenolic content (TPC), antioxidant activity (DPPH· and ABTS·), and tannin composition (hydrolysable and condensed). In addition, LC-MS-DAD was used for semiqualitative purposes to detect vescalagin/castalagin and vescalin/castalin, as well as gallic acid and ellagic acid. The developed valorization protocol allows the efficient fractionation and recovery of the major polyphenolic components of CW with a sustainable approach that also evaluates pre-industrial scaling-up

Exhausted Woods from Tannin Extraction as an Unexplored Waste Biomass: Evaluation of the Antioxidant and Pollutant Adsorption Properties and Activating Effects of Hydrolytic Treatments

Exhausted woods represent a byproduct of tannin industrial production processes and their possible exploitation as a source of antioxidant compounds has remained virtually unexplored. We herein report the characterization of the antioxidant and other properties of practical interest of exhausted chestnut wood and quebracho wood, together with those of a chestnut wood fiber, produced from steamed exhausted chestnut wood. 2,2-Diphenyl-1-picrylhydrazyl (DPPH) and ferric reducing/antioxidant power (FRAP) assays indicated good antioxidant properties for all the materials investigated, with exhausted chestnut wood, and, even more, chestnut wood fiber exhibiting the highest activity. High efficiency was observed also in the superoxide scavenging assay. An increase of the antioxidant potency was observed for both exhausted woods and chestnut wood fiber following activation by hydrolytic treatment, with an up to three-fold lowering of the EC50 values in the DPPH assay. On the other hand, exhausted quebracho wood was particularly effective as a nitrogen oxides (NOx) scavenger. The three materials proved able to adsorb methylene blue chosen as a model of organic pollutant and to remove highly toxic heavy metal ions like cadmium from aqueous solutions, with increase of the activity following the hydrolytic activation. These results open new perspectives toward the exploitation of exhausted woods as antioxidants, e.g., for active packaging, or as components of filtering membranes for remediation of polluted waters

Correction: Exhausted Woods from Tannin Extraction as an Unexplored Waste Biomass: Evaluation of the Antioxidant and Pollutant Adsorption Properties and Activating Effects of Hydrolytic Treatments. Antioxidants 2019, 8, 84

The authors wish to make the following corrections to their paper [...