A Review on Sources,Extractions and Analysis Methods of a Sustainable Biomaterial:Tannins

Condensed and hydrolysable tannins are non-toxic natural polyphenols that are a commercial commodity industrialized for tanning hides to obtain leather and for a growing number of other industrial applications mainly to substitute petroleum-based products.They are a definite class of sustainable materials of the forestry industry.They have been in operation for hundreds of years to manufacture leather and now for a growing number of applications in a variety of other industries,such as wood adhesives,metal coating,pharmaceutical/medical applications and several others.This review presents the main sources,either already or potentially commercial of this forestry by-materials,their industrial and laboratory extraction systems,their systems of analysis with their advantages and drawbacks,be these methods so simple to even appear primitive but nonetheless of proven effectiveness,or very modern and instrumental.It constitutes a basic but essential summary of what is necessary to know of these sustainable materials.In doing so,the review highlights some of the main challenges that remain to be addressed to deliver the quality and economics of tannin supply necessary to fulfill the industrial production requirements for some materials-based uses.

Role of tannin pretreatment in flotation separation of magnesite and dolomite

Flotation separation of magnesite and its calcium-containing carbonate minerals is a difficult problem.Recently,new regulat-ors have been proposed for magnesite flotation decalcification,although traditional regulators such as tannin,water glass,sodium carbon-ate,and sodium hexametaphosphate are more widely used in industry.However,they are rarely used as the main regulators in research because they perform poorly in magnesite and dolomite single-mineral flotation tests.Inspired by the limonite presedimentation method and the addition of a regulator to magnesite slurry mixing,we used a tannin pretreatment method for separating magnesite and dolomite.Microflotation experiments confirmed that the tannin pretreatment method selectively and largely reduces the flotation recovery rate of dolomite without affecting the flotation recovery rate of magnesite.Moreover,the contact angles of the tannin-pretreated magnesite and dolomite increased and decreased,respectively,in the presence of NaOl.Zeta potential and Fourier transform infrared analyses showed that the tannin pretreatment method efficiently hinders NaOl adsorption on the dolomite surface but does not affect NaOl adsorption on the magnesite surface.X-ray photoelectron spectroscopy and density functional theory calculations confirmed that tannin interacts more strongly with dolomite than with magnesite.

Biochemistry and transcriptome analysis reveal condensed tannins alleviate liver injury induced by regulating cholesterol metabolism pathway

Free cholesterol has been considered to be a critical risk factor of nonalcoholic fatty liver disease(NAFLD).It remains unknown whether dietary intake of condensed tannins(CTs)have distinguishable effects to alleviate liver damage caused by a high cholesterol diet.Male C57BL/6 mice were fed a high cholesterol diet for 6 weeks,and given CTs treatment at a dosage of 200 mg/(kg·day)at the same time.The results indicated that compared with mice fed a normal diet,a high cholesterol diet group resulted in significant weight loss,dysregulation of lipid metabolism in blood and liver,and oxidative stress in the liver,but CTs treatment dramatically reversed these negative effects.Hematoxylin and eosin(H&E)staining and frozen section observation manifested that CTs treatment could effectively reduce the deposition of liver cholesterol and tissue necrosis caused by high cholesterol intake.CTs alleviated liver injury mainly by regulating the expression of related genes in cholesterol metabolism pathway and AMPK phosphorylation.Our results confirmed that CTs have remarkable cholesterol lowering and anti-liver injury effects in vivo.

Overview of the Synthesis, Characterization, and Application of Tannin-Glyoxal Adhesive for Wood-Based Composites

More than a century after its initial synthesis,urea-formaldehyde(UF)resins still have dominant applications as adhesives,paints,and coatings.However,formaldehyde in this industry produces formaldehyde emissions that are dangerous to health.Scientists have spent the last decade replacing formaldehyde and phenol with environmentally friendly substances such as glyoxal and tannin to create bio-based adhesives.This review covers recent advances in synthesizing glyoxal tannin-based resins,especially those made from sustainable raw material substitutes and changes made to synthetic processes to improve mechanical properties.The efficacy of using tannin-glyoxal adhesives in producing wood-based composites has been proven.The glyoxylate reaction forms cross-linked bridges between the aromatic sites of the tannin and glyoxal molecular structures.Glyoxal tannin adhesive with a greater percentage of glyoxal than tannin will produce an adhesive with better characteristics.The gel time reduces as the hardener concentration rises from 7.5%to 15%when glyoxal is used in adhesives.However,excessive amounts of glyoxal will result in a decrease in viscosity values.Glyoxal exhibits faster delivery degradation when it reaches a maximum temperature of approximately 130°C,although it initiates the curing process slightly slower at 110°C.Adding glyoxal to tannin-based adhesives can improve the mechanical properties of composite boards.The wet shear strength of the resulting plywood is increased by 105.4%with the addition of 5-weight percent tannin-based resin with glyoxal as a cross-linker in Soy Protein Adhesive.With glyoxal as a hardener,the panels produced showed good internal bond strengths(>0.35 MPa)and met the international standard specifications for interior-grade panels.

Structural Elucidation of the Polymeric Condensed Tannins of Acacia nilotica Subspecies by ^(13)C NMR, MALDI-TOF and TMA as Sources of Bioadhesives

Tannin was extracted from different subspecies of Acacia nilotica,Acacia nilotica nilotica(Ann),Acacia nilotica tomentosa(Ant)and Acacia nilotica adansonii(Ana).The aim was to elucidate their structure and evaluate their reactivity as bioadhesives in the wood industry.The extracts were prepared by hot water extraction(90°C tem-perature).Their gel time with paraformaldehyde was used atfirst to compare their reactivity.The tannin contents and the percentage of total polyphenolic materials in different solutions of the extracts spray dried powder were determined by the hide powder method.Concentrated solutions(47%)were tested by both MALDI ToF,13CNMR.The thermomechanical analysis(TMA)was performed to evaluate their modulus of elasticity(MOE)at different pHs.The gel times of all the three tannin extracts showed that their reactivity and it was com-parable to other known procyanidin/prodelphinidin tannin extract types.Ana,Ann and Ant showed highest per-cent of total polyphenolic materials at 70%,64%,and 57%,respectively.The 13CNMR spectra showed that the three subspecies of condensed tannins were mainly constituted of procyanidins(PC)and prodelphinidins(PD)in slightly different ratios.Ann(56.5%PC and 43.4%PD),Ant(57%PC and 43%PD)and Ana(58%PC and 42%PD).MALDI–TOF spectra showed the presence offlavonoid monomers,and oligomers some of which linked to short carbohydrates monomers or dimers.TMA revealed that the three types of tannins had high MOE at their initial pH(5).

Tannins from Acacia mangium Bark as Natural Dyes for Textiles:Characteristics and Applications

Tannins are capable of producing natural dyes with antioxidant and antibacterial propertis,while synthetic dyes are commonly used in the textile industry,causing environmental issues like water pollution.This research aims to utilize waste tannins as natural dyes as an alternative to synthetic dyes.This study examined the effect of the extraction method on tannin properties such as phenolic content,antioxidants,and antibacterial activity.In addition,Pyrolysis Gas Chromatography‒Mass Spectrometry(Py-GCMS)analysis was used to identify the effect of extraction temperature on the chemical elucidation of tannin.The effect of tannin concentration was evaluated against four bacteria that are usually found on human skin:Staphylococcus epidermidis,Bacillus subtilis,Propionibacterium acnes,and Staphylococcus aureus.Extraction temperature significantly influences the chemical composition of tannin,which leads to different antioxidant properties.The maximum antibacterial properties of tannin were obtained at 90℃with the inhibition zone in the range of 0.9–1.0 mm against four bacteria,tannin yield of 26.59%,Gallic Acid Equivalents or total phenolic content(GAE)of 40.30 mg/g,and Radical Scavenging Activity or antioxidant activity(RSA)of 89.88%.Moreover,the concentration of tannin was significantly linear with its antibacterial properties.Tannin was successfully applied to the textile by using alum as a mordanting agent to create an antibacterial textile.The textile’s bacterial structure damage was analyzed under Field Emission Scanning Electron Microscopy(FESEM).After 50 washings,tannin-textiles with alum-modified properties remained stable compared to those without alum,with S.aureus and S.epidermidis being the most vulnerable bacteria,as confirmed by FESEM images.Hence,tannin is a feasible alternative to harmful and nondegradable synthetic dyes and antibacterial agents.

Matrix Assisted Laser Desorption Ionization Time of Flight(MALDI-TOF)-Mass Spectrometry and^(13)C-NMR-Identified New Compounds in Paraberlinia bifoliolata(Ekop-Beli)Bark Tannins

Extracts of plant origin,particularly tannins,are attracting growing interest for the sustainable development of materials in the industrial sector.The discovery of new tannins is therefore necessary.The aim of this work was to contribute to the understanding of the properties of Paraberlinia bifoliolata tannin by Matrix Assisted Laser Desorption Ionization Time of Flight Mass Spectroscopy MALDI-TOF/MS and Carbon 13 Nuclear Magnetic Resonance(13C NMR).The chemical composition of tannin extracted from Paraberlinia bifoliolata bark was determined,as was the mechanical strength of the resin hardened with Acacia nilotica extracts.Yield by successive water extraction was 35%.MALDI-TOF/MS analysis revealed the presence of three new compounds in this tannin,previously unknown in this family of extracts.These are 3-hydroxyproline acid,N-methyl-4-hydroxypipecolic acid and N-methyl-5-dihydroxypipecolic acid.The identification of the above molecules means that this tannin can be used for industrial applications,as a resin in the manufacture of particleboard and in the formulation of green corrosion inhibitors.This information is reinforced by 13C NMR spectrometry,which indicates the presence of several polyflavonoid units,confirming the condensed nature of the tannin.Thermomechanical analysis of the resin formed by the purified tannin of Paraberlinia bifoliolata to which a vegetal biohardener has been added provided a Modulus of Elasticity(MOE)value of 4840 MPa at 150℃,confirming its possible use as a binder resin in the manufacture of wood panels as well as for the formulation of a corrosion inhibitor.

Shear Resistance of Siltous Sands Improved with Bridelia Tannins

The ruin of several civil engineering works occurs due to shear rupture of the ground. When the stress is greater than the shear resistance, the internal friction angle and the cohesion of the soil loosen and rupture occurs. Cement and lime are often used to stabilize soils and improve soil strength. The costs and environmental problems of these technologies raise concerns and challenge researchers to innovate with clean, inexpensive materials, accessible to the most disadvantaged social classes. The question that this study seeks to answer is whether the binders derived from plant tannins, which also stabilize soils, improve the shear resistance of these soils. To do this, we determined for silty sand the shear parameters, notably the cohesion and the angle of internal friction in the non-stabilized state and when they are stabilized with the powder of the bark of the Bridelia under different water states. The results show that the addition of Bridelia powder to silty sand increases the cohesion of the soil by nearly 70.71% and the friction angle by 4.31%. But in unfavourable water conditions, the cohesion and internal friction angle of the silty sand material improved with Bridelia bark powder drops drastically by nearly 81.56%. but does not dissolve completely as for the same material. When it is not stabilized. This information is an invaluable contribution in the search for solutions to increase the durability of earthen constructions by improving the water-repellent properties of soils.

Composite Panels from the Combination of Rice Husk and Wood Chips with a Natural Resin Based on Tannins Reinforced with Sugar Cane Molasses Intended for Building Insulation: Physico-Mechanical and Thermal Properties

The objective of this work is to develop new biosourced insulating composites from rice husks and wood chips that can be used in the building sector. It appears from the properties of the precursors that rice chips and husks are materials which can have good thermal conductivity and therefore the combination of these precursors could make it possible to obtain panels with good insulating properties. With regard to environmental and climatic constraints, the composite panels formulated at various rates were tested and the physico-mechanical and thermal properties showed that it was essential to add a crosslinker in order to increase certain solicitation. an incorporation rate of 12% to 30% made it possible to obtain panels with low thermal conductivity, a low surface water absorption capacity and which gives the composite good thermal insulation and will find many applications in the construction and real estate sector. Finally, new solutions to improve the fire reaction of the insulation panels are tested which allows to identify suitable solutions for the developed composites. In view of the flame tests, the panels obtained are good and can effectively combat fire safety in public buildings.

Tannin-Based Biofoams-A Review

This review details the development of tannin-based biofoams for fire resistance and acoustic insulation and details the different varieties of these foams that have been developed,from tannin-furanic self-blowing foams to tannin-furanic polyurethanes and finally non-isocyanate tannin-basedcarbohydrates polyurethanes(NIPU).

Covalent and Ionic Bonding between Tannin and Collagen in Leather Making and Shrinking:A MALDI-ToF Study

Collagen powder hydrolysates were reacted with a solution of commercial mimosa bark tannin extract.The mixture was prepared at ambient temperature and prepared at 80°C to determine what reactions,if any,did occur between the collagen protein through its amino acids and the polyphenolic condensed tannin.The reaction products obtained were analyzed by matrix assisted laser desorption ionization time-of-flight(MALDI ToF)mass spectrometry.Reactions between the two materials did appear to occur,with the formation of a relatively small proportion of covalent and ionic linkages at ambient temperature but a considerable proportion of covalent linkages tannin-protein amino acids and the disappearance of ionic bonds.The linkages between the two materials appeared to be by amination of the phenolic–OHs of the tannin by the amino groups of the non-skeletal side chains of arginine,and by esterification by the–COOH groups of glutamic and aspartic acid of the aliphatic alcohol-OH on the C3 site of the flavonoid units heterocycle of the tannin.The proportion of covalent linkages increases markedly and predominate with increasing temperatures.This tightening of the tannin-protein covalent network formed may be an additional contributing factor both to leather wear resistance and performance as well to leather shrinking when this is subjected to excessive temperatures.

Chemistry and ecological significance of tannins

This paper summarized of the chemistry characteristics of tannins and their various adverse effects onmammalian herbivore, including the chemical nature of hydrolyzable and condensed tannins, their analysis mathods, and the tannins antifeedant mechanisms.

Self-Cross-Linked Tannin-Aminated Tannin Surface Coatings for Particleboard

Aminated tannins were prepared by reacting mimosa condensed tannin extract with ammonia yielding the substitution of many,if not all of the tannin hydroxyl groups with–NH_(2)groups.A tannin-aminated tannin(ATT)particleboard coating was then prepared by reacting raw tannin extract with aminated tannin extract and thus cross-linking the two by substituting tannin’s hydroxyl groups with the–NH_(2)groups on the aminated tannin to form–NH-bridges between the two.The resulting particleboard coating gave encouraging results when pressed at 180℃for 3 min.Conversely,the system in which tannin was reacted/cross-liked with urea(ATU)by a similar amination reaction did not perform as well as the ATT system,and this even when a higher curing temperature and longer hot press time were used.In particular its water repellence was worse probably due to the presence of urea and such a system with lower reactivity.Nonetheless,substituting the tannin–OHs with the urea–NH_(2)groups appeared to also take place.ATT gave better results than ATU as regards water repellence and mechanical resistance as shown by the cross cut test.The ATT system was shown to be between 95%and 98%biosourced.The difference appeared to be due,by TMA analysis,to the much faster formation of the ATT hardened network leading to a better cross-linked polymer coating.The chemical species formed for both the ATT and ATU system were studied by MALDI ToF and CP MAS^(13)C NMR.

Lead Removal from Aqueous Solutions Using Novel Gel Adsorbent Synthesized from Natural Condensed Tannin

Lead has caused serious environmental pollution due to its toxicity, accumulation in food chains and persistence in nature. In this paper, removal of lead from aqueous solutions is investigated using a novel gel adsorbent synthesized from natural condensed tannin. The novel adsorbent performs in aqueous solutions as a weak base with valid basic groups of 1.2mmol·g-1 tannin gel particles and therefore results in the elevation of pH value of aqueous solutions. Even when initial pH is 3.6, final pH at equilibrium can climb up to 6.5 that is above the pH value for Pb(OH)2 precipitation formation and then lead can be removed from wastewater by this so-called surface precipitation. The adsorption isotherm can be expressed by the Langmuir equation and the maximum capacity for adsorption of Pb is up to 92 mg·g-1 (based on dry adsorbent) when initial pH value is 3.6. Hence, the adsorbent does offer favorable properties in lead removal with respect to its high adsorption capacity at low initial pH value, which is advantageous to lead removal from acidic wastewater. A model is put forward to describe the individual adsorption phenomenon of the tannin gel adsorbent.

Hydrolysable Chestnut Tannin Extract Chemical Complexity in Its Reactions for Non-Isocyanate Polyurethanes(NIPU)Foams

Non-isocyanate polyurethane(NIPU)foams from a commercial hydrolysable tannin extract,chestnut wood tannin extract,have been prepared to determine what chemical species and products are taking part in the reactions involved.This method is based on two main steps:the reaction with dimethyl carbonate and the formation of urethane bonds by further reaction of the carbonated tannin with a diamine-like hexamethylene diamine.The hydroxyl groups on the tannin polyphenols and on the carbohydrates intimately linked with it and part of a hydrolysable tannin are the groups involved in these reactions.The carbohydrate skeleton of the hydrolysable tannin is also able to participate through its hydroxyl groups to the same two reactions rendering the whole molecular complex able to react to form NIPUs.The analysis by Matrix-Assisted Laser Desorption Ionization(MALDI-TOF)mass spectrometry and 13C Nuclear Magnetic Resonance(13C NMR)to further investigate the reaction mechanisms involved revealed the unsuspected complexity of chestnut hydrolysable tannin,with different fragments reacting in different manners forming a hardened network of considerable complexity.As the morphology and performance of these types of foams changes slightly with the change in the amount of glutaraldehyde and hexamine hardeners,the best performing foam formulation previously determined was scanned by SEM and analysed chemically for the structures formed.

Self-Blowing Non-Isocyanate Polyurethane Foams Based on Hydrolysable Tannins

ABSTRACT Non-isocyanate polyurethane(NIPU)foams using a hydrolysable tannin,also vulgarly called tannic acid,namely here commercial chestnut wood tannin extract was prepared.Compression strength did not appear to depend on the foam apparent density while the formulation composition of the NIPU foams has been shown to be more determinant.These NIPU foams appeared to be self-extinguishing once the high temperature flame is removed.The ignition time gave encouraging results but for improved fire resistance the foams may need some fire-retardant addition.FTIR spectrometry showed the formation of non-isocyanate urethane linkages.Thermogravimetric analysis indicated a good thermal resistance of these foams,with thermal degradation following four phases.First in the interval 25℃–120℃ range,mainly evaporation of water occurs with a maximal loss of 10%weight.In the 150℃–450℃ temperature range foams mass loss is of almost 70%.In particular in the 125℃–275℃ range occurs the degradation of some small molecular weight substances.In the 500℃–790℃ temperature range the foams do not present any further large degradation.

Kinetics of non-catalyzed hydrolysis of tannin in high temperature liquid water

High temperature liquid water(HTLW) has drawn increasing attention as an environmentally benign medium for organic chemical reactions,especially acid-/base-catalyzed reactions. Non-catalyzed hydrolyses of gallotannin and tara tannin in HTLW for the simultaneous preparation of gallic acid(GA) and pyrogallol(PY) are under investigation in our laboratory. In this study,the hydrolysis kinetics of gallotannin and tara tannin were determined. The reaction is indicated to be a typical consecutive first-order one in which GA has formed as a main intermediate and PY as the final product. Selective decomposition of tannin in HTLW was proved to be possible by adjusting reaction temperature and time. The present results provide an important basic data and reference for the green preparation of GA and PY.

Tannin–Phenol Formaldehyde Resins As Binders for Cellulosic Fibers: Mechanical Properties

In this study Eucalyptus tannin (T) was isolated from outer bark of Eucalyptus trees;as sodium phenoxide salt and used as extender or copolymer into phenol formaldehyde (PF) resin at five percent (10, 20, 30, 40 and 50)% W/W. Tan-nin-phenol formaldehyde (TPF) and tannin formaldehyde-phenol formaldehyde (TFPF) resins that synthesized in this study were evaluated as adhesive material for cellulosic fibers by study the mechanical properties of the composite sheets .The results show that the substituting of (PF) with tannin at (10 –50)% W/W give resins with mechanical properties comparable or near to those of pure (PF) , where the tensile strength at break (Tb) ranging from 15.15 Mpa to 22.27 Mpa as compared with 17.6 Mpa for pure (PF);while the impact strength properties (Im) of composites sheets increased with increased the (T) percents which were about 5.16 KJ/m2 for (TPF – 10%) and 7.21 KJ/m2 for (TPF - 50%) .On the other hand modification of (T) to tannin formaldehyde resin (TF) appear less performance at the results of this study , this effect probably to low penetration of (TFPF) resins between the small voids of cellulose fibers when soaked it in resin solutions. In general the results of this study indicate that the Eucalyptus tannin can be used for par-tial substitution of (PF) to produce resins with feasible mechanical properties and can be used in some applications of (PF) resins.

Removal of lead from aqueous solutions by condensed tannin gel adsorbent

Lead has caused serious environmental pollution due to its toxicity, accumulation in food chains and persistence in nature. In this paper, lead removal from aqueous solutions was investigated using condensed tannin gel adsorbent synthesized from a natural tannin compound. It is found that the adsorption is strongly affected by pH values of aqueous solutions. Within pH range of 3 5—6, when initial lead concentration is 100 mg/L, removal efficiency is more than 90%. Adsorption equilibrium is reached within 150 minutes. The adsorption isotherm fits well with the Langmuir equation, by which the saturated adsorption uptake of 190 mg Pb 2+ /g dry tannin gel adsorbent is obtained. By means of thermodynamics analysis, it is revealed that the process is exothermic and the adsorption heat is up to 38 4 kJ/mol. With respect to high efficiency, moderate pH requirement and minimized second pollution, the tannin gel adsorbent exhibits a promising potential in the removal of lead from wastewater.

A Review of Soy-Tannin Gelling for Resins Applications

Soy flour(SF),soy protein and soy protein isolates(SPI)have been the focus of increasing research on their application as new materials for a variety of applications,mainly for wood adhesives and other resins.Tannins too have been the focus of increasing research for similar applications.While both materials are classed as non-toxic and have achieved interesting results the majority of the numerous and rather inventive approaches have still relied on some sort of hardeners or cross-linkers to bring either of them or even their combination to achieve acceptable results.The paper after a presentation of the two materials and their characteristics concentrates on the formation of gels,gelling and even hardening in the case of soy-tannin combined resins.The chapter than finishes with details of the formation of resins giving suitable wood adhesive of acceptable performance by the covalent coreaction of soy protein and tannin without any other hardener,thus totally bio-sourced,non-toxic and environment friendly as a base of further advances to expect in future by these two materials combination.