(PDF) Review On Tannins Extraction Processes, Applications and Possibilities 11
(PDF) Review On Tannins Extraction Processes, Applications and Possibilities 11
(PDF) Review On Tannins Extraction Processes, Applications and Possibilities 11
Authors:
Md Nazrul Islam
Khulna University
Md Ashaduzzaman
Khulna University
Citations 63
Reads 3,444
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Review
A R T I C L E I N F O A B S T R A C T S
Article History: Tannins are found in most of the species throughout the plant kingdom, where their functions are to protect
Received 12 March 2020 the plant against predation and might help in regulating the plant growth. There are two major groups of
Revised 12 August 2020 tannins, i.e., hydrolyzable and condensed tannins. The tannins are being used as important and effective
Accepted 17 August 2020
chemicals for the tanning of animal hides in the leather processing industry since the beginning of the indus-
Available online xxx
try. Additionally, the tannins have been using as mineral absorption and protein precipitation purposes since
Edited by J Gr
uz 1960s. These are also used for iron gall ink production, adhesive production in wood-based industry, anti-
corrosive chemical production, uranium recovering chemical from seawater, and removal of mercury and
Keywords:
methylmercury from solution. Presently, tannins are considering as bioactive compound in nutrition science.
Tannins
It has also been considered for advanced applications, i.e., 3D printing and biomedical devices. The applica-
Extraction
tion of tannins as medicine is another new dimension in medical science. This paper outlines the general
Applications
Potentials information about tannins followed by their extraction process. The utilization of tannins has also been pre-
sented in a broader scale. Depending on all these information, the article also describes the impending utili-
zation of tannins for ensuring high-sustainability and better environmental performance.
© 2020 SAAB. Published by Elsevier B.V. All rights reserved.
1. Introduction Scalbert, 2000). Tannins act as plant defensive agents, protect trees
from fungi, pathogens, insects and herbivorous animals (De Bruyne
The word "tannin" originates from the ancient Celtic word for oak et al., 1999; Hagerman et al., 1998; Khanbabaee and van Ree, 2001;
and was introduced by Seguin to explain the ability to convert hide Sharma, 2019).
or skin into leather by a plant extract in 1796 (Hagerman, 2002). Gen- Broadly, tannins are categorized into two main groups, i.e., con-
erally, tannins are obtained from natural renewable resources, i.e., densed tannins and hydrolyzable tannins. Condensed tannins are
plants (Pizzi, 2008; Ramakrishnan and Krishnan, 1994) which are the composed of flavonoids (flavan 3-ol or flavan 3, 4-diol) without a
secondary phenolic compounds of plants (Hagerman, 2002; Sharma, sugar core, however, the hydrolyzable tannins are composed of ella-
2019). More specifically, tannins are either galloyl esters or oligo- gic and gallic acids with a sugar core mainly glucose (Khanbabaee
meric and polymeric proanthocyanidins (Khanbabaee and van Ree, and van Ree, 2001; Sharma, 2019). Among the different types of tan-
2001) produced by the secondary metabolism of plants (Hagerman, nins, hydrolyzable tannins have limited sources in the nature com-
2002; Lewis and Yamamoto, 1989), i.e., synthesized by biogenetic pared to condensed tannins (Haslam, 1982; Hillis, 1985). Thus,
pathways (Lewis and Yamamoto, 1989). Proanthocyanidins are the condensed tannins are dominating the world market consisting
results of polyketide (malonyl-CoA) and phenylpropanoid metabo- more than 90% of the total commercial tannins (Filgueira e t al.,
lism and gallic acids are formed from shikimate directly (Lewis and 2017; Pizzi, 2008). According to Pizzi (2006), the total annual
Yamamoto, 1989). Tannins are the main polyphenolic secondary extraction of tannin was 200,000 t worldwide of which 90% was
metabolites distributed widely in the range of 5 to 10% of dry vascular condensed tannins. Tannins are extracted with water alone or by
plant materials (Barbehenn and Constabel, 2011) found mainly in mixing with other solvents like methanol, ethanol, acetone,
bark, stems, seeds, roots, buds, and leaves (Barbehenn and Constabel, NaOH. The solid to solvent ratio and the extraction temperature
2011; Giovando et al., 2019; Tomak and Gonultas, 2018). Tannins are are very important for the extraction of tannins (Arinaa and Hari-
also available in foodstuffs, i.e., grapes, blackberries, strawberries, suna, 2019; Dentinho et al., 2020; Duraisamy et al., 2020; Luo et
walnuts, cashew nuts, hazelnuts, mangoes and tea (Clifford and al., 2019; Martins et al., 2020; Naima et al., 2015; Poaty et al.,
2010; Rhazi et al., 2019). Alongside, the particle size also influen-
* Corresponding author. ces the extraction process. Antwi-Boasiako and Animapauh
E-mail address: [email protected] (A.K. Das). (2012) reported that hot water extraction process provided better
https://doi.org/10.1016/j.sajb.2020.08.008
0254-6299/© 2020 SAAB. Published by Elsevier B.V. All rights reserved.
A.K. Das et al. / South African Journal of Botany 135 (2020) 5870 59
results. However, according to Duraisamy et al. (2020) and Med- Ree, 2001). Acid hydrolysis of hydrolyzable tannins helps to get gallic
ini et al. (2014), the extraction was better when methanol-water acid, ellagic acid or other similar species (Haslam, 2005). On the other
solvent was used. hand, condensed tannins are composed of flavolans or polymers of
Tannins are mainly used by the leather industry for both hide flavan-3-ols (catechins) and/or flavan 3:4-diols (leucoanthocyani-
treatment and the color of leather since past centuries (Kemppainen dins) (Hillis, 1997; Kemppainen et al., 2014). Compare to the hydro-
et al., 2014; Pizzi, 2008). However, the phenolic structure of tannins lyzable tannins, condensed tannins have a wide range of molecular
has the potentiality to use in other applications like adhesives for weight ranging from 500 to over 20,000 (Haslam and Cai, 1994; Jiang
wood industry (Pizzi, 2006), insulating foams (Tondi et al., 2009), et al., 2002), and have the ability to react with aldehydes to generate
mineral industry, wine production industry, animal nutrition, oil polymeric materials (Jiang et al., 2002). Phlobaphene, a water insolu-
industry (Pizzi, 2006), water treatment plant (Combs, 2016) and pro- ble product, is possible to produce by polymerization of condensed
tecting metal from corrosion (Luo et al., 2019; Ostovari et al., 2009). tannins. Char, an important wood-based product, yield is higher in
The extracted tannins can also be used as adhesive, biocide and fungi- condensed tannins compared to hydrolyzable tannins as it has con-
cide, which could open a new dimension for the wood-based indus- densed structure (Sebestyen et al., 2019). The tannins are widely dis-
try (Ogunwusi, 2013). It has also the potentiality to make proteins tributed in many species of plants. Plant species that contain higher
and other polymers like pectin (Ramakrishnan and Krishnan, 1994) amount of condensed tannins are wattle, quebracho, mangrove and
apace with the use in medical science (Ogawa et al., 2018; Ogawa hemlock, whereas chestnut and myrobalan species contain higher
and Yazaki, 2018). All these applications make tannins an important amount of hydrolyzable tannins (Hillis, 1997).
green biochemical which attracts researchers nowadays (Carrieri et
al., 2016; Combs, 2016; Ghahri and Pizzi, 2018; Nath et al., 2018;
3. Extraction of tannins
Ogawa et al., 2018; Shirmohammadli et al., 2018).
Researchers are substantially working on the extraction and
Tannins have attracted significant attention because of its variety
application of tannins (Arinaa and Harisuna, 2019; Chen et al., 2020a,
of potential applications, and have considerable abundance in nature.
2020b; Liao et al., 2020; Martins et al., 2020; Naima et al., 2015; Poaty
However, its amount in plant depends on the geography, biological
et al., 2010; Zhang et al., 2019). Depending on those studies, there are
origin, species, populations, age and position in the tree, i.e., inner or
some comprehensive reviews which deals mainly with the structure
outer wood of trees (Pizzi and Cameron, 1986; Puech et al., 1999).
and role of tannins on animal and human health (Bele et al., 2010;
Considering the potential applications, tannin-related researches
Bernhoft, 2010; Chung et al., 1998; Clauss, 2003; Feng et al., 2013;
have undergone a great boost; however, due to tannins heteroge-
Hassanpour et al., 2011; Kraus et al., 2003; Rowe and Conner, 1979;
neous nature, the extraction process remains as the main challenges
Schofield et al., 2001; Serrano et al., 2009; Versari et al., 2013). How-
for their valorization. The extraction of tannins is not done in a single
ever, there is no extensive review particularly on the extraction of
protocol, and the procedures are widely variable. Because of the
tannins with its applications. Thus, this review paper aims to provide
extraction process, the extracted tannin contains different types of
a wide-ranging insight into the topic including the extraction pro-
impurities including minerals, stilbenes and sugars (Bimakr et al.,
cess, current uses and the potential applications of tannins.
2011; Kemppainen et al., 2014). For instance, the presence of carbo-
hydrate in tannins reduce its anti-fungal efficacy (Anttila et al., 2013;
2. Tannins Hmidani et al., 2019) as well as create problems during impregnation
into wood for preservation (Anttila et al., 2013; Yalcin and Ceylan,
The term tannin is widely applied to a complex large biomolecules 2017). Additionally, the amount of impurities depends on the proc-
of polyphenolic nature having sufficient hydroxyls and other suitable essing parameters like particle size, temperature, pressure, time, sol-
groups such as carboxyls to form strong complexes with various mac- vent type, and solid to solvent ratio. Bello et al. (2020), Bimakr et al.
romolecules (Fig. 1). They are commonly found in both gymnosperms (2011) and Hmidani et al. (2019) reported that temperature and solid
and angiosperms and are categorized as condensed and hydrolyzable to solvent ratio controlled the carbohydrate content in the extracted
tannins (Khanbabaee and van Ree, 2001; Navarrete et al., 2013; Saad tannins. Hence, the extraction of tannins should be done carefully by
et al., 2014). The hydrolyzable tannins contain glucose or other poly- controlling the operation parameters precisely.
hydric alcohols esterified with gallic acid (gallotannins) or hexahy- In general, tannins are extracted either by hot water or water
droxydiphenic acid (ellagitannins) (Hobbs, 2008; Kemppainen et al., along with other solvents from the plant materials, i.e., bark, wood,
2014). Depending on the esterification, hydrolyzable tannins are sub- stem, leaf. Acetone (Baaka et al., 2017; Bimakr et al., 2011; Dentinho
divided into gallotannins and ellagitannins (Khanbabaee and van et al., 2020; Hmidani et al., 2019; Kotze and Eloff, 2002; Meng et al.,
Fig. 1. Structure of (A) hydrolyzable and (B) condensed tannins (Raja et al., 2014).
60 A.K. Das et al. / South African Journal of Botany 135 (2020) 5870
2019; Poaty et al., 2010; Scalbert et al., 1989; Wurger et al., 2014), 2020). When methonaol/ethanol was used with water as sovents, the
disopropyl ether, ethyl acetate, ethyl ether (Kotze and Eloff, 2002), temperature ranged between 60 and 120 °C (Case et al., 2014;
methanol (Case et al., 2014; Romero et al., 2020), ethanol ((Naima et Romero et al., 2020), however, higher temperature showed better
al., 2015; Rhazi et al., 2019), sodium sulphite (Poaty et al., 2010) and results. I n case of NaOH a s solvent, t he best temp erature wa s
NaOH (Antwi-Boasiako and Animapauh, 2012; Guo et al., 2020) were 82 °C for the extraction of tannins from bark (Naima et al., 2015;
used by different researchers as solvent with or without water. Den- Rhazi et al., 2019). This processing temperature was lower (room
tinho et al. (2020) used acetone to extract tannins from dried leaves temperature to 60 °C) when the acetone was used as solvent for
and green stems of rockrose (Cistus ladanifer), whereas 75% methanol the extraction of tannins (Dentinho et al., 2020; Luo et al., 2019).
with water was used to extract tannins from pine (Pinus radiata) Pressure application helps to extract tannins at lower tempera-
barks (Case et al., 2014; Romero et al., 2020). In other studies, 50 to ture (Bianchi et al., 2014b) as well as the advance technologies
80% methanol was used to extract tannin from fever tree (Acacia xan- like ultrashound, microwave technology remain lower processing
thophloea) (Duraisamy et al., 2020) and marsh rosemary (Limonium temperature (Luo et al., 2019; Naima et al., 2015; Rhazi et al.,
delicatulum) (Medini et al., 2014). Naima et al. (2015) and Rhazi et al. 2019). However, the size of the particles play a significant role in
(2019) used different method to extract tannin from black wattle the extraction process.
(Acacia mollissima) barks called microwave technology where water, For efficient extraction, these plant parts are grounded prior to
80% methanol and 80% ethanol were used for infusion and macera- any type of extraction (Antwi-Boasiako and Animapauh, 2012; de
tion. Besides, methanol (60%) was also used with ultrasound technol- Hoyos-Martinez et al., 2019). However, the particle size varies
ogy to extract tannins from acorn (Luo et al., 2019). The authors of depending on other parameters like efficacy level, time, temperature,
those studies reported that methanol extraction provided more solvent type, raw materials type, and process. Antwi-Boasiako and
yield compared to the water extraction (Duraisamy et al., 2020; Animapauh (2012) used barks and wood chips to extract tannins
Medini et al., 2014)(Medini et al., 2014; Duraisamy et al., 2020). from it having the particle size of 0.5 mm and 0.55 mm, respec-
NaOH was also used for tannin extraction from mussoorie berry tively. Different researchers extracted tannins from different plants
(Coriaria nepalensis) and 0.22% concentration among the different by using different solvents where they used different particle sizes as
NaOH concentrations showed the best results (Gou et al., 2020 ). illustrated in Table 1. Tannins extraction is quicker when the particle
n-hexane has also been used to extract tannins, however, the size is smaller (Case et al., 2014; Luo et al., 2019; Romero et al., 2020)
yield is the lowest, thus, it is not at all a popular method of because solvents penetrates in to the particle easily which shorten
extraction (de Hoyos-Martinez et al., 2019). Addition of additives the extraction time.
like enzymes, acids with solvent positively influence the quality Besides the aforementioned tannin extraction techniques, there
and amount of tannins. According to a study, it was observed are many other advanced techniques including super critical, ionic
that the addition of enzyme in the solvent enhanced the tannins liquid assisted microwave, infrared-assisted and pressurized hot
contents in the solution (Gao et al., 2019; Osete-Alcaraz et al., water extraction technique. In the pressurized water extraction
2020). The authors used poly galacturonase and pectin-lyase with method, 374 °C temperature and 22.1 MPa pressure are used (de
grape skin for tannin extraction. Enzymes can degrade the cell Hoyos-Martinez et al., 2019; Ersan et al., 2018). Ionic liquids, i.e., 1-
wall and cause pore formation, and thus, the release of tannins ethyl-3-methylimidazolium Br, 1‑butyl‑3-methylimidazolium Br, 1-
from grape skin can be increased (Arnous and Meyer, 2010; Li et hexyl-3-methylimidazolium Br, 1-octyl-3-methylimidazolium Br, 1-
al., 2006; Osete-Alcaraz et al., 2020; Pinelo et al., 2006). Similarly, decyl-3-methylimidazolium Br, 1‑butyl‑3-methylimidazolium Cl,
0.01% ascorbic acid with 70% acetone also positively influenced 1‑butyl‑3-methylimidazolium BF4, 1‑butyl‑3-methylimidazolium
the extraction of total tannins, condensed tannins and phlorotan- NO3, and 1‑butyl‑3-methylimidazolium OH have been used as a pre-
nins from mi croalgae ( Petchidurai et al., 2019). However, among treatment prior to microwave extraction (Yang et al., 2012). In infra-
the different methods, hot water extraction method is still popu- red-technique, infrared lam is used to heat during extraction. The
lar and commonly used for the extractions of tannins in the efficiency of this method depends on the wavelength of the infra-
industry (Fraga-Corral et al., 2020; Kemppainen et al., 2014) as red heater, distance between source of infrared and material, and
well as in th e laborat ory (Tascioglu et al., 2013). The simplicity of the solvent (Cai et al., 20 11; Chen et al., 2010; Escobedo et al.,
the method a nd its lower co st are the main r easons for it s popu- 2016). Extraction of tannins by gamma radiation has also been
larity. Moreover, some of the researchers even reported that the studied. For this technique, specific solvent s are requir ed to soak
amount of extracted condensed and hydrolyzable tannins were the material. On the other hand, materials and solvents can be
the highest when the solvent was hot water (Antwi-Boa siako and irradiated by gamma radiation as well (Santos et al., 2011).
Animapauh, 2012). This might be related with the processing Supercritical is another modern technology for extracting tannins
parameters of tannins extraction like species, types of raw mate- where supercritical solvents, i.e., carbon dioxide, butane, pentane,
rials, particle size, temperature and time. Types of solvent and its fluorinated hydrocarbons, sulfur hexafluoride and nitrous oxide
temperature also influence the extraction, which might have are used. Co-solvent or modifier is used to improve the selectivity
impact on the total volume of extraction. However, the tempera- of CO2 (Ashraf-Khorassani and Taylor, 2004; de Hoyos-Martinez
ture varies depending on the raw materials, process of extraction, et al., 2019; Ersan et a l., 2018; Talmaciu et al., 2016; Wang and
time and particle size. Weller, 2006; Yepez et al., 2002).
Bello et al. (2020) extracted tannin from spruce (Picea abies) barks The extraction efficiency and the quality of tannins depend on the
by hot water method having the temperature of 85 °C, however, it duration of the extraction (Hussain et al., 2020; Luo et al., 2019), i.e.,
was 90 °C when condensed tannins was extracted from pine (Pinus long extrction durtion yields higher amount of tannins. The cell struc-
radiate) barks (Hussain et al., 2020). Depending on the solvent type, ture of plant is destroyed with time in the solvents, and the yield of
this temperature can be as high as 120 °C. Even with water as solvent, tannin extraction is increased (Petchidurai et al., 2019), however,
higher temperature (105 °C) was used when tannins were extracted quality might decrease with time. Solvent-to-solid ratio is another
from red angico (Anadenanthera macrocarpa), jabuticaba (Myrciaria important factor which governs the tannins extraction process (Den-
jabuticaba) and umbu (Spondias tuberosa) barks (Martins et al., 2020). tinho et al., 2020; Gou et al., 2020). Continuous mixing of solvents
On the other hand, the optimum temperature was 75 °C when tan- with the particles also helps the extractioin process, and better mix-
nins were extracted from galls of manjakani (Quercus infectoria) (Ari- ing is possible when there is higher solvent-to-solid ratio. However,
naa and Harisuna, 2019). It was obsreved that the use of water as the this ratio modifies the particles but not for the solvent governing the
solvent for extraction required lower temperature (Duraisamy et al., extraction of tannins.
Table 1
Different types of extraction methods practiced to extract tannins from different species using different types of solvents.
Acetone-water Soxhelt and rotating shaker 50 10 3 h shaking at 120 rpm Bark Bay berry Petchidurai et al. (2019);
Rotating shaker 28 -30 10 Whole part Brown, green and red Meng et al. (2019)
algae
Rotating shaker and centrifuge 1 h shaking, centrifuge at
3200 rpm for 10 min
Bowl Room 24 Wash (petroleum ether) Sawdust Oak Poaty et al. (2010)
Bowl, stirrer Room 48 1:10 (solid to solvent), closed Leaves and stems Rockrose 1 mm Dentinho et al. (2020)
container, stirring
Bowl, stirrer 60 2 Stirring at 150 rpm Rice straw <1 mm Shi et al. (2020)
Acetone-ethanol Bowl 24 Leaves Guava Mailoa et al. (2013)
Methanol-water Ultrasound 0.04 Ultrasound with enzyme Acorn 2001000 mm Luo et al. (2019)
addition
A.K. Das et al. / South African Journal of Botany 135 (2020) 5870
62 A.K. Das et al. / South African Journal of Botany 135 (2020) 5870
Table 2
Sources and applications of condensed tannins studied by different researchers.
Leather processing Higher shrinkage temperature, resis- Babul, quebracho and wattle Mahdi et al. (2009); Gustavson (1947);
tance to detannage in leather industry Lipsitz et al. (1949); Hathway (1962)
Fishing net Preservation Bacterial and fungal resistant Black cutch tree, Brazilian mahogany, Hathway (1962)
spurred mangrove barks, red man-
grove barks
Plastic and Wood adhesive Better strength properties of wood com- Quebracho, black wattle, maritime pine, Hathway (1962); Knowles and
posites, better adhesive properties, bay berry, larch, grape, western hem- White (1954); Li et al. (2019b);
superior water resistance properties lock, red cypress pine, Australian Liu et al. (2020); Nico (1950);
mangrove Cui et al. (2015); El Hage et al. (2011);
Lei et al. (2008); Hafiz et al. (2020);
Yang et al. (2019); Ping et al. (2011a);
Ping et al. (2011b); Ping et al. (2012);
Dalton (1950); MacLean and Gard-
ner (1952); Hathway (1962);
Janceva et al. (2011);
Plomley et al. (1957); Pizzi (2008)
Oil and ceramics industry Controlling viscosity of mud, and Quebracho O'Flaherty et al. (1956); Hathway (1962)
increase the suspending power of the
casting slip
Anticorrosive for metal Protection against corrosion Quebracho, black wattle, mangrove Byrne et al. (2019); Byrne et al. (2020);
Nardeli et al. (2019);
O'Flaherty et al. (1956);
Shah et al. (2011)
Wood preservation Protection against fungus and termite, Black wattle, quebracho, and Turkish Tascioglu et al. (2012);
protection against of preservative pine, valonia, chestnut, tara, and Oak Tascioglu et al. (2013); Tomak and
Gonultas (2018);
Thevenon et al. (2010)
Wood properties improvement Improved dimensional stability of wood Quebracho, black wattle, patula pine Yalcin and Ceylan (2017); Bariska and
Pizzi (1986)
Fire-resistance of wood Improve fire resistance property Black wattle Tondi et al. (2012)
Water and waste water Higher coagulation efficiency, methylene Norway spruce, wattle Bello et al. (2020); Wang et al. (2019);
treatment plant blue and heavy metals absorbent Grenda et al. (2020);
Grenda et al. (2018); Combs (2016);
Wang et al. (2019)
Packaging Anti-oxidant, UV-shielding Quebracho Li et al. (2019c)
Animal food Nutritional Red quebracho, rockrose, black wattle, Costes-Thire et al. (2019a);
chestnut Costes-Thire et al. (2019b);
Dentinho et al. (2020); Lima et al.
(2019); Aguerre et al. (2016);
Aguerre et al. (2020)
3D printing Good printing quality Black wattle Liao et al. (2020)
A.K. Das et al. / South African Journal of Botany 135 (2020) 5870 63
The binding of tannins with collagens is dependent on tempera- resistant properties of adhesives for plywood were prepared by mix-
ture, pH and molecular weight of tannins (Valls et al., 2009). Though ing paraformaldehyde, filler and sulfited tannin solutions obtained
tannin materials are dissimilar based on pH, salt content and natural from Eucalyptus crebra, wattle extract and quebracho extract (Dalton,
conditions of acid content, these can be controlled maintaining 1953; Knowles and White, 1954). Adhesives prepared from Austra-
proper conditions (Cheshire, 1946; Miekeley, 1935). pH of tan liquors lian mangrove tannins in addition with a small proportion of com-
is relatively high due to the absence of higher amount of phenolic mercial phenol-formaldehyde, resorcinol-formaldehyde, or phenol-
acids in condensed tannins, and tannins are not carboxylated by and resorcinol-formaldehyde complied with Australian and British
themselves. Salt content of tannin materials varies depending mainly standard for synthetic adhesives for plywood (Hathway, 1962; Jan-
on the species and location, which contributes to the salt in tannin ceva et al., 2011; Plomley et al., 1957). Adhesives for corrugated card-
liquors. Mangrove plants tannins contain sodium chloride, whereas board were also prepared from the extracted tannins of wattle (Pizzi,
quebracho extracts possess sodium sulfate (Hathway, 1962). Acacia 2008). Researchers also produced novel adhesive by using polyethy-
nilotica tannin with aluminum sulfate is used to produce leather, and lenimine and condensed tannins which showed better water resis-
this tannage has shown good cross-linking with collagens (Mahdi et tance properties having superior shear strength properties of wood
al., 2009). composites (Li et al., 2004). Tannins obtained from Acacia nilotica
along with formaldehyde had the ability to use as wood-based adhe-
sives. The presence of B-ring of catechol A. nilotica tannins can
4.1.2. Preservation of fishing net
increase the network formation, which enhances the strength prop-
Preservation of fishing nets by various condensed tannins is popu-
erties of the composite (Osman, 2012).
lar in the Indo-Pacific countries. This process prevents the degrada-
tion of cellulose by bacterial and fungal cellulases. Fishing nets are
4.1.4. Oil and ceramics industry
submerged in hot tannin solution, and is repeated for several times
Condensed tannins are also commonly used in the oil and ceramic
for getting better preservation. Tannin-impregnated nets are further
industries. In the bentonite oil-well muds in the United States, the
treated with either hot copper sulfate or dichromate solution for
main problem is the flow and suspension characteristics of bentonite.
some cases (Atkins, 1936; Steven, 1950) for better stability of the tan-
Tannins help to reduce the viscosity and increase the flow of benton-
nins in net and its durability. The water solubility of tannin can be
ite (Hathway, 1962). Quebracho tannins are used widely to control
reduced by oxidation. Copper sulfate or dichromate solution can oxi-
the viscosity of the mud, and the annual consumption is around
dize the tannins and fix them with net (Cecily and Kunjappan, 1971,
30,00040,000 tons for this purpose only (O'Flaherty et al., 1956). In
1973). Condensed tannin materials used as fishing net preservative
the United States, it is accounted for about 40% of the total tannins
are extracted from Burma cutch from Acacia catechu heartwood,
consumption in 1950 (Anderson, 1955; Panshin et al., 1950).
Malayan (mangrove) cutch from Carapa obovata and Ceriops candol-
Scientist reviewed the incorporation of condensed tannins by the
leana barks, and Borneo(mangrove) cutch from Ceriops candolleana,
ceramic industry. Quebracho tannins enable the use of higher solid
Rhizophora candelaria, and Rhizophora mucronata barks (Hathway,
mixer in the casting of clay slip by lowering the viscosity of the clay-
1962).
water mixes. Condensed tannins save the plaster molds from deterio-
ration by increasing the tensile strength of clay casts and eliminating
4.1.3. Preparation of plastics and adhesives the silica from the mixture, with consequent saving the deterioration
Condensed tannins are phenolic raw materials, which react with of plaster molds. Quebracho tannins enhance the suspending power
formaldehyde and these can be used for the production of synthetic of the slip for the casting of bone in China (Hathway, 1962).
resins (Bianchi et al., 2014a; El Hage et al., 2011; Hafiz et al., 2020;
Hathway, 1962; Lei et al., 2008; Yang et al., 2019). Nico (1950) stud- 4.1.5. Anticorrosive chemical for metals
ied the suitability of quebracho-formaldehyde resins for the produc- Tannins protect the iron materials from sulfate-reducing bacteria
tion of adhesives and plastics. Molded plastics were produced by by exerting a bacteriostatic action (Farrer et al., 1953; Kusmierek and
pressing the mixtures of quebracho and wattle tannins, paraformal- Chrzescijanska, 2015). Mangrove tannins are economically viable to
dehyde, and plasticizer having the exact amount. The products satis- protect the underground iron pipes and tubes (O'Flaherty et al.,
fied all the required properties such as stability and water resistance 1956; Shah et al., 2011). Condensed tannins have flavan-3-ol, which
as per the specifications of British Standards when phenol-formalde- has oxygen atoms in its functional groups and aromatic rings, and
hyde was used (Hathway, 1962; Knowles and White, 1954). The aromatic ring can scavenge oxygen and inhibits corrosion (Gerengi
hydroxyl groups of tannins can cross-linking with different com- and Sahin, 2012; Gerengi et al., 2012). The free electrons of oxygen
pounds, i.e., formaldehyde for preparing adhesives and plastics (Hafiz get protonated in acidic media and the molecules of the protonated
et al., 2020; Santos et al., 2014; Wahab et al., 2014). constituent are adsorbed on the metal surface because of electrostatic
Many researchers have studied the applications of condensed tan- interaction and this inhibits the corrosion of metal (Singh et al., 2012,
nins for the production of plywood and particle-board adhesives (Cui 2010). Tannate films of tannin extracts are formed on iron and steel
et al., 2015; Fechtal and Riedl, 1993; Ghahri and Pizzi, 2018; Hall et surfaces to protect it from atmospheric corrosion (Byrne et al., 2019;
al., 1960; Heinrich et al., 1996; Herrick and Bock, 1958; Kim and Kim, Knowles and White, 1954). Similarly, for aluminum, a protective film
2004; Li et al., 2019b; Liu et al., 2020; Narayanamurti and Das, 1958; is formed during the submersion of aluminum in tannin solutions
Narayanamurti et al., 1957; Nath et al., 2018; Pichelin et al., 2006; and it reduces the active surface area, and inhibits o xygen reduc-
Pizzi, 2009, 1979, 1983; Plomley et al., 1976; Santos et al., 2017; Vaz- tion and metal dissolution. Thus, it can be used for the preserva-
quez et al., 2012). Tannins help to make greater adhesion between tion of aluminum as well (Byrne et al., 2020; Nardeli et al., 2019;
fibers and matrix, and achieve better physical and mechanical prop- Stratta et al., 1956).
erties of the wood-based composites (Hafiz et al., 2020; Tondi et al.,
2012; Wahab et al., 2014). Sauget et al. (2013) used mimosa tannin as 4.1.6. Preservation of wood
adhesive for the production of fiber biocomposites, and reported Condensed tannins can be used as wood preservative (Laks, 1987;
good physical and mechanical properties. However, adhesives pre- Thevenon et al., 2010). Condensed tannins help to protect wood from
pared from Tsuga heterophylla, Acacia mollissima and Callitris calcar- fungal attack and increase the durability of wood (Thevenon et al.,
ata barks showed less strength but higher water-resistance 2010; Tomak and Gonultas, 2018) as it works in the living plants.
properties compared to the commercial adhesives (Dalton, 1950; Scalbert et al. (1988) have mentioned that the phenolic compounds
MacLean and Gardner, 1952). Strong bondability and better water- of tannins help to protect wood from rots of any kinds. Tannins along
64 A.K. Das et al. / South African Journal of Botany 135 (2020) 5870
with hexamine evolves with wood (Kamoun et al., 2003; Pichelin et efficiency than anionic dyes, like, tartrazine and alizarin violet. On
al., 2006), and maintains the mobility of boron with less leaching out the other hand, cationic adsorbent has a high efficacy for many
to work as a fungicide (Pizzi and Baecker, 1996). Again, condensed anionic dyes, even for a cationic dye, such as, methylene blue (Combs,
tannins contain cathechol and epicathecin, which have ability to sup- 2016). Anionic compounds, like, 2,4-D, MCPA, clofibric acid, acetylsa-
press the fungal activity (Hirasawa and Takada, 2004; Ichihara and licylic acid, ketoprofen, diclofenac, naproxen are absorbed effectively
Yamaji, 2009; Tascioglu et al., 2012, 2013; Tomova et al., 2005; Veluri whereas cationic products, such as, amoxicillin, atrazine and trimeth-
et al., 2004; Yamamoto et al., 2000) and increase the durability of oprim are adsorbed ineffectively (Combs, 2016). The use of con-
wood. Condensed tannins prevent wood from photodegradation by densed tannins (Wattle tannins) in the composite of cellulose
quenching 1 O2 and suppressing phenoxyl radicals (Chang and Chang, microfibers can absorb methylene blue efficiently. The tannins pro-
2018). vide binding site to absorb the methylene blue. Therefore, this can be
used for sewage water treatment (Wang et al., 2019).
4.1.7. Properties improvement of wood
Application of tannin-based formulation (tannin, hexamethylen- 4.1.10. Packaging
tetramine, sodium hydroxide, phosphoric acid and boric acid) in Condensed tannin can also be used for the packaging materials.
wood enhanced the bending, compression and hardness properties The use of 5 wt% quebracho tannins with cellulose nanofiber showed
of scots pine and beech wood by around 20%. The tannin formulation better tensile strength, thermal stability, ultraviolet (UV)-shielding
makes a reticulation in the cells of wood, which helps to reinforce the ability and anti-oxidant biohybrid film. This film was used as the
mechanical properties of wood (Tondi et al., 2012). Besides, con- packaging material for food and other related materials (Li et al.,
densed tannins make a covalent bond with hemicellulose (Bariska 2019c). Phenolic units of tannin help to absorb UV (Li et al., 2019c),
and Pizzi, 1986) and proteins (Bariska and Pizzi, 1986; Capparucci et thus, the materials get protection against UV rays. Again, phenolic
al., 2011), which strengthen or plasticize the cell walls and improve units suppress the hydroxyl radical formation by donating reducible
the strength properties of wood (Bariska and Pizzi, 1986). Yalcin and hydrogen atoms (Andrade et al., 2005; Gulcin et al., 2010) and thus,
Ceylan (2017) concluded that tannins obtained from quebracho and tannin can work as anti-oxidant. On the other hand, the formation of
mimosa impregnated into the wood with different varnish coating, good electrostatic attraction between cellulose and tannin enhances
which increased the protection of wood against different abiotic and both thermal stability and tensile strength properties of tannin-cellu-
biotic factors. Tannins also improve the dimensional stability of wood lose biohybrid film (Li et al., 2019c).
(Militz and Homan, 1994).
4.1.11. Animal food
4.1.8. Improving the fire-resistance properties of wood Condensed tannins help to utilize protein in the animal body by
The tannin formulation (tannin, hexamethylentetramine, sodium controlling the gastrointestinal parasites. Thus, condensed tannins
hydroxide, phosphoric acid and boric acid) used to improve the wood are beneficial to animal health (Coop and Kyriazakis, 1999; Hoste et
properties also improves the fire-resistance properties of wood. The al., 2012; Juhnke et al., 2012; Lisonbee et al., 2009; Santos et al.,
presence of phosphoric acid and boric acid in the formulation helps 2020). Costes-Thire et al. (2019a, 2019b) found that the use of que-
to improve the properties. The impregnation of tannin formulation bracho tannins extracted from quebracho tree (Schinopsis lorentzii) in
reduced the ember time of scots beech wood by ten times (Tondi et the diet of sheep contributed the optimum utilization of protein by
al., 2012). Tannin as well as hexamine works as an anchor to develop controlling Haemonchus contortus parasite. Dentinho et al. (2020)
a network with wood cell (Kamoun et al., 2003; Pichelin et al., 2006) used condensed tannin of Cistus ladanifer in the soybean meal for the
and reduces the leaching out of the boron (Pizzi and Baecker, 1996). sheep and observed that the protein of soybean meal digested
Therefore, tannin and boron work together to protect wood against completely. The controlling of rumen protozoa was observed after
fire. incorporating tannins obtained from Mimosa tenuiflora in the diets of
sheep by Lima et al. (2019). Additionally, quebracho tannins and
4.1.9. Water and waste water treatment plant chestnut tannins in the diets of cow were also used to increase the
Tannins have the potentiality to use as the water treatment chem- milk protein and decrease the nitrogen content in the urine (Aguerre
icals (Ibrahim and Yaser, 2019; Meng et al., 2019; Ohara, 1994). Con- et al., 2016, 2020).
densed tannins work as coagulant, which is used for treating
wastewater. The condensed tannins extracted from Picea abies barks 4.1.12. 3D printing
showed better coagulation efficiency compared to quebracho tannins In the recent days, condensed tannins are used in the 3D printing.
(Bello et al., 2020). For better efficacy, the authors modified the both Liao et al. (2020) observed that around 20% acetylated condensed
types of tannins following Mannich reaction with diethanolamine or tannin in poly lactic acid (PLA) and tannin filament composite pro-
ethanolamine and formaldehyde. The condensed tannins obtained vided good printing quality with better tensile property. For this
from Acacia mearnsii also showed better efficiency for removal of case, the authors modified the mimosa tannins by using acetic anhy-
anionic and cationic dyes from the wastewater (Grenda et al., 2020, dride in the presence of 1 wt% catalyst - pyridine.
2018). Tannic acid is used in dye industry and water treatment pro-
cess for purifying water (Ramakrishnan and Krishnan, 1994). Tannin- 4.2. Applications of hydrolyzable tannins
based commercial products are available in the market and are used
to eradicate suspended colloidal matter like clay and organic matter. Hydrolyzable tannins are also used for various works. These tan-
Chelating ability of tannin is important to remove the metallic ions, nins make complex interactions with protein. Thus, it has the ability
i.e., Cr, Ni, Zn or Cd from waste water (Hobbs, 2008). to use for animal nutrition and industrial processing (Cadahia et al.,
A. mearnsii cryogel obtained from the extraction of A. mearnsii tan- 1996). This section discusses the applications of hydrolyzable tannins
nin with formaldehyde in alkaline medium is used as absorbent for and these are summarized in Table 3.
heavy metal. Extraction of A. mearnsii tannin by epichlorohydrin in N,
N-dimethylformamide medium, followed by grafting with diethyle- 4.2.1. Leather processing industry
netriamine and triethylamine yields as a cationic adsorbent. This cat- For leather manufacturing process, the conversion of animal hide
ionic absorbent is also used for the removal of heavy metals from or skin into leather is considered as the main art of tanning in leather
water (Combs, 2016). A. mearnsii cryogel is also applicable for the industries. To provide leather, tannin cross-links with the collagen
removal of dyes. It is noted that cationic dyes have higher adsorption chains located in the hide during tanning process. Hydrolyzable
A.K. Das et al. / South African Journal of Botany 135 (2020) 5870 65
Table 3
Sources and applications of hydrolyzable tannins studied by different researchers.
Leather processing Strong surface properties Masuri berry Guo et al. (2020)
Plastic resin and adhesives Superior water resistance properties, exterior Chestnut Ghahri and Pizzi (2018); Vazquez et al. (2012);
applications Vazquez et al. (2013); Spina et al. (2013)
Wood preservation Fungal protective Chestnut, tara Tomak and Gonultas (2018)
Wine quality improvement Improve wine flavor Oak ao et al. (2005); Puech et al. (1999); Viriot et al.
Jord~
(1993); Vivas and Glories (1996); Vivas et al. (1996)
Anti-corrosion agents for metals Tara Byrne et al. (2019)
Medication Antimutagenic, anticancer, antioxidant, reduction of Ong et al. (1995); Smeriglio et al. (2017); Yugarani et al.
cholesterol (1993)
* (-) indicates that related information are not available in the respective literature.
tannins obtained from plant extract are also widely used for tanning 4.2.5. Anti-corrosion agents for metals
in leather industries (Ramakrishnan and Krishnan, 1994). Guo et al. Tannins can be used as anticorrosion agent for mild steel and cast
(2020) found that the hydrolyzable tannins obtained from Coriaria iron. The rusted steel is treated with mimosa tannins since 1976
nepalensis can make stable cross-linking with the collagen fibers of (Hobbs, 2008). Sulfonated tannins are used to remove scale forming
leather, which provides strong surface properties. The quality of the in the cooling water pipes and boilers. In the protective coating
leather in terms of shrinkage, elongation at break, tear strength and industry, tannins are used for protecting metal surfaces as a primer/
tensile strength was comparable with the commercially available undercoat/topcoat (Hobbs, 2008). Hydroxyl aromatic ring of hydro-
valonia tannin reagents. lyzable tannins scavenges oxygen and inhibits corrosion by blocking
the metal surface through adsorption which enhances inhibition
(Ostovari et al., 2009). Thus, the tannins can be used as anticorrosive
4.2.2. Preparation of plastic resin and adhesives to reduce or replace inorganic components, which are not environ-
Gallic acid used for manufacturing of plastic resins ((Ramak- mentally friendly. Caesalpinia spinosa tannins were used for protect-
rishnan and Krishnan, 1994) and adhesives (Ramakrishnan and ing metals from corrosion (Byrne et al., 2019).
Krishnan, 1994; Vazquez et al., 2013) can be used to produce differ-
ent types of composites. Ghahri and Pizzi (2018) studied the effec- 4.2.6. Medication
tiveness of hydrolyzable tannin as adhesive for particleboard. The Biological activities of hydrolyzable tannins confirm the beneficial
cross-linking of tannin by formaldehyde in the reaction of polycon- effect of it on human health. It is used as antimutagenic, anticancer
densation can provide exterior category wood adhesive (Ghahri and and antioxidant. Further, hydrolyzable tannins help to diminish
Pizzi, 2018; Pizzi, 2009). Spina et al. (2013) concluded that hydrolyz- serum cholesterol and triglycerides, and suppress lipogenesis by
able tannins can be used as adhesive for particleboard which can insulin (Ong et al., 1995; Smeriglio et al., 2017; Yugarani et al., 1993).
replace a significant portion of synthetic phenol from phenol-formal- Table 3
dehyde resin.
5. Potential uses of tannins
4.2.3. Preservation of wood Properties of tannins have made them to consider for using in var-
Hydrolyzable tannins can be used as wood preservative and thus, ious purposes. It has the potential to use for various purposes such as,
increase the durability of wood by protecting against fungal attack leather processing industry, wood industry, anti-corrosion of metal,
(Barry et al., 2001; Pizzi and Baecker, 1996; Tomak and Gonultas, water treatment plant, animal food, medical science and the produc-
2018). Other researchers reported that tannin could protect wood tion of advanced materials. Tannins are the major tanning material
against rots (Scalbert et al., 1998). These tannins with hexamine for converting animal hide/skin into leather. Actually, inorganic salts
anchor in wood (Kamoun et al., 2003; Pichelin et al., 2006) and con- especially chrome salts are used to produce 7085% leather. Replac-
trol the mobility of boron resulting lower leaching of it and act as fun- ing of toxic chrome salts with less toxic and environmentally friendly
gicide (Pizzi and Baecker, 1996). Adiitionally, the gallic acid of tanning materials is possible by polymerization of tannins with other
hydrolyzable tannins reduces the fungal activity (Tascioglu et al., synthetic materials (Hobbs, 2008).
2012, 2013) and increases the durability of wood. Efficient extraction of tannins might also help to reduce the use of
synthetic toxic materials. Most of the wood-based industries use
adhesives and synthetic adhesives are hazardous to environment
4.2.4. Improvement of wine quality (Hobbs, 2008). There are several patents related to the tannins-based
Tannins play a great role on the quality of wine (Motta et al., 2020; bioadhesive (Hobbs, 2008) which have confirmed the efficacy of con-
Paissoni et al., 2020; Vignault et al., 2020). Hydrolyzable tannins con- densed tannins as bioadhesives for composites industries (Kim and
tain polyphenols and antioxidant, which influence the wine quality Kim, 2004; Pichelin et al., 2006). However, the main limitations of
(Motta et al., 2020). The tannin extracted from oak heartwood is com- the adhesives are higher molecular weight, higher degree of poly-
monly used to increase the flavor of wine in the wine industry. merization, complex composition and slower rate of reaction (Liu et
Besides, ellagitannins play a great role for controlling the color and al., 2020). Thus, solving these issues by nucleophilic reagent acidoly-
flavor of wine during its aging (Puech et al., 1999). These tannins dif- sis (Li et al., 2019b; Mouls and Fulcrand, 2015), sulfite treatment
fuse into the wine with the aging of wine in barrels (Jord~ ao et al., (Xiang-ming et al., 2007), mercaptoethanol treatment under acidic
2005; Peng et al., 1991; Viriot et al., 1993; Vivas and Glories, 1996; condition (Li et al., 2019a) and NaOH/urea treatment (Liu et al., 2020)
Vivas et al., 1996) and help to increase the organoleptic quality of can help to use tannins as adhesives by the wood-based industries.
wine (Jord~ao et al., 2005). Ellagitannins also involve in the oxidation The tannin-modified phenolic resin or tannin alone can provide bet-
process of red and white wine (Moutounet et al., 1989) which absorb ter strength properties with lower or zero formaldehyde emission (Li
the dissolved oxygen quickly and facilitate the hydroperoxidation of et al., 2019b, 2004; Liu et al., 2020; Osman, 2012). Therefore, tannins
the constituents (Vivas and Glories, 1996). can be used as alternative source of adhesive in wood composite
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