Accepted Manuscript

Recent advancements in natural dye applications: A review

Mohammad Shahid, Shahid-ul-Islam, Faqeer Mohammad

PII: S0959-6526(13)00169-8
DOI: 10.1016/j.jclepro.2013.03.031
Reference: JCLP 3368

To appear in: Journal of Cleaner Production

Received Date: 23 June 2012

Revised Date: 15 March 2013
Accepted Date: 17 March 2013

Please cite this article as: Shahid M, Shahid-ul-Islam , Mohammad F, Recent advancements in natural
dye applications: A review, Journal of Cleaner Production (2013), doi: 10.1016/j.jclepro.2013.03.031.

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Recent advancements in natural dye applications: A review

Mohammad Shahid, Shahid-ul-Islam and Faqeer Mohammad*

*Corresponding author

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Department of Chemistry,

Jamia Millia Islamia (A Central University),

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New Delhi-110025, India

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Phone: +91-9350114878. E-mail: faqeermohammad@rediffmail.com

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Abstract

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A vast array of colorants obtained from natural sources such as plants, insects/animals
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and microbes have been scrutinized in recent past for their use in different kinds of

applications. Research into new natural dyes sources along with eco-friendly, robust and cost-
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effective technologies for their processing and application have greatly aided in widening the
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scope of natural dyes in various traditional and advanced application disciplines. This review
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encompasses a summary of research performed in last fifteen years (1998-2013) in different

arenas of applications of natural dyes, with specific reference to technological development

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in natural textile dyeing and use of natural dyes in functional finishing of textiles, food
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coloration and dye sensitized solar cells. In addition, some newly discovered applications of

natural dyes have also been discussed.

Keywords: Natural Dyes; Mordants; Protective textiles; Dye Sensitized Solar Cells; Food

coloration

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1. Introduction

With the publics enhanced cognizance to eco-safety and health concerns, environmentally

benignant and non-toxic bioresource products are regaining popularity in different spheres of

our lives. Natural dyes, obtained from plants, insects/animals and minerals, are renewable and

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sustainable bioresource products with minimum environmental impact and known since

antiquity for their use, not only in coloration of textiles (Kadolph, 2008) but also as food

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ingredients (Dweck 2002) and cosmetics (Frick, 2003). With the discovery of synthetic

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colorant mauve by W. H. Perkin in 1856 and subsequent upsurge in research, production

and application of synthetic dyes, use of natural colorants slumped sharply (Holme, 2006).

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However, the application of a number of synthetic dyes has detrimental effects on

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environment and associated allergic, toxic, carcinogenic, harmful responses. Amidst growing

environmental and health concerns eco-friendly non-toxic natural dyes re-emerged as a

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potential viable Green chemistry option as an alternative/co-partner to some extent to

synthetic dyes (Yusuf et al., 2011; Mirjalili et al., 2011). Recent resurgence in research and
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development on natural dye production and application is observed due to increasing

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popularity of more natural lifestyle based on naturally sustainable goods (Grifoni et al.,

2009). Natural flora/fauna is full of exquisite colors fascinating and attracting human being
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towards a vast portfolio of possibilities (Dawson et al., 2009). A large number of plant and

animal/insect sources have been identified for extraction of color (Guinot et al., 2006; Kumar
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and Sinha, 2004) and their diversified use in textile dyeing (Samanta and Agarwal, 2009) and
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functional finishing (Gupta et al., 2005), food coloration (Delgado-Vargas, 2000), cosmetics

(Dweck 2002), Dye-sensitized solar cells (Hao et al., 2006), histological staining (Tousson,

and Al-Behbehani, 2011), pH indicator (Mishra et al., 2012) and several other application

disciplines (Kushwandi et al., 2012; Zyoud et al., 2011). During the last few decades,

increasing attention has been paid by researchers to various aspects of natural dye

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applications (Fig. 1) and extensive R&D in this area is underway worldwide. This review

article is intended to collect the dispersed information, from 1998 to 2013, about the recent

developments in traditional and newly discovered applications of natural dyes. Special focus

has been given to the technological development in natural textile dyeing and use of natural

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dyes in functional finishing of textiles, food coloration and dye sensitized solar cells.This

review article also highlights a number of issues which should be targeted to make natural

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dyes a viable co-partner/alternative to synthetic dyes.

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2. Technological advancements in textile coloration with natural dyes

Coloration is an integral part of ever expanding complex chemical wet processing of textiles,

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which involves use of many types of chemical entities and physico-chemical processes.

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Environmental concerns arising due to accelerated development in textile wet processing

industry paved the way for ongoing interest in the development of cleaner production
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strategies for making cost effective value added textile products (Ahmed and El-Shishtawy,

2010).
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Hill (1997), while discussing lack of quality research work on natural dyeing techniques
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cited, Our knowledge of dyeing techniques and recipes is gleaned from printed books and

dye house records and can be reconstructed and adapted. In last fifteen years, investigations
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about possible use of natural dyes in textile dyeing processes performed by various research

groups have changed the scenario to greater extent and relatively superior and sophisticated
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information on natural dyeing techniques are available today.

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Natural dyeing in textiles is currently of great interest in both research fields as well as textile

industries due to increasing attention to the aspects of water pollution, sustainability of raw

materials and processed products, biodegradability and environment-friendly attributes

(Bechtold et al., 2009). Studies on dyeing techniques were attempted by using both

conventional exhaustion method (Ali et al., 2009) as well as non-conventional methods such

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as ultrasonic (Kamel et al., 2005), microwave (Nourmohammadian and Gholami, 2008), pad

dyeing (Mongkholrattanasit, 2010; Ratnapandian et al., 2012), High temperature High

Pressure (HTHP) dyeing (Bhattacharya and Lohiya, 2002), contact dyeing (Kadolph and

Casselman, 2004) and other optimized methods. As a result, many research articles have been

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published dealing with re-establishment of traditional dyeing techniques (Mikropoulou et al.,

2009; Zarkogianni et al., 2011), variabilities of natural sources for dyeability (Bhuyan and

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Saikia, 2005; Sharma et al., 2012a), processing improvement for natural colorant extraction

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(Bechtold et al., 2002; Sivakumar et al., 2011), approaches to the improvement of color

fastness or dyeing characteristics for the naturally dyed fabrics, adaptation and optimization

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of natural dyeing methods and use of modern day technologies in different stages of natural

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textile dyeing process (Nasirizadeh et al., 2012; Samanta, and Agarwal, 2009). Any process

based on use of natural dyes will have to consider the environmentally sound processing
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techniques and the overall process must be competitive with regard to the use of chemicals,

energy, wastes and waste water and overall costs (Bechtold and Mahmud-Ali, 2008).
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2.1. Mordants and mordanting

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Dyeing of fabrics with natural dyes often leads to problems such as narrow shade range, and

lower color fastness of the dyed textiles. Attempts to overcome these problems have been
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mainly focused on the use of mordants. In addition to creating affinity between dye and fibre,

the use of mordants also change the hue of certain dyes. Different mordants used with the
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same dye may darken, brighten or drastically alter the final color of the dyed fibre (Manhita
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et al., 2011; Yi and Cho, 2008). Colorimetric properties of the dyed fabrics such as Lightness

(L*), redness-yellowness (a*), blueness- greenness (b*), chroma (c*), hue (ho) and colour

strength (K/S) are greatly dependent on the chemical nature of mordants and fibers and the

metal ion complex forming ability with the dye and the fiber (Tang et al., 2010). Mordanting

generally improved dye performance and help the dyer to achieve a broad spectrum of colors

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on a wide range of natural as well as synthetic fibres with expanded shade ranges and better

fastness properties (Kadolph and Casselman, 2004). Samanta and Agarwal (2009) presented a

comprehensive review of studies available on different types of mordants, mordanting

methods and their effects on natural dyeing for a variety of textile materials. Most commonly

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used mordants in natural dyeing are aluminium potassium sulfate, potassium dichromate,

stannous chloride, ferrous sulphate and copper sulfate (Samanta and Agarwal, 2009).

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Improving traditional mordanting processes and selecting new mordants to replace traditional

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heavy-metal ions has been an important part in the development of natural dyeing of textiles.

Several other metallic salt mordants were also attempted with satisfactory results on lab scale

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(Table 1). Zheng et al. (2011) have successfully employed rare earth chlorides as mordant for

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the dyeing ramie fabrics with natural dyes. Results showed that rare earth metals would be a

kind of promising environment friendly mordants in natural dyeing in comparison with the
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commonly used metallic salts in the present era of environment consciousness, as using rare

earth chlorides as mordants greatly reduced the ionic concentration in natural dyeing.
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Natural dyeing processes typically generate wastewater containing residual toxic metal ions
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from metal salt mordants which have negative impact on the environment and public health

(Burkinshaw and Kumar, 2009; Zheng et al., 2011). The content of metal ions in textile
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products and effluent discharged from textile industries is strictly prohibited beyond a certain

specified limit. Alum and ferrous sulphate are considered safest among metallic salt mordants
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and tin can be used up to certain limits while use of chrome and copper is almost banished
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considering their toxic nature (Savvidis et al., 2013; Zarkogianni et al., 2010). While dyeing

with natural dyes, a substantial proportion of mordant remains unexhausted in the residual

dyebath and thus may pose serious effluent problems, hence, it is important to pay special

attention to the limit values of metal ions in textiles and effluents prescribed by

Environmental Protection Regulations.

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Considering above environmental concerns, use of natural mordants (Table 2) in place of

metallic salt mordants is also advised by some researchers. Although, the concept of natural

mordanting is not new; yet the lack of well documented research records on their application

downplays their role in real time natural textile dyeing. Biomordant sources are either plants

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with high tannin content (Prabhu and Teli, 2011) or metal hyperaccumulating plants

(Cunningham et al., 2011). Recently chlorophyll extracted from different plant sources has

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also been successfully employed as biomordant (Guesmi et. al., 2012). Vegetable tannins are

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water soluble polyphenolic compounds found in wide variety of plant parts such as bark

wood, fruit, fruit pods, leaves, roots and plant galls. Phenolic hydroxyl groups of tannins

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enable them to form effective crosslinks with different types of fibers and dyes and help in

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color fixation. Tannin based mordants were found most effective in case of cotton fibre

which has very low affinity for most of the natural dyes (Prabhu and Teli, 2011).
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Cunningham et al. (2011) presented a detailed review on reasons for selecting different Al-

hyperaccumulating plants as natural metallic mordants and their application in natural dyeing
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of traditional Indonesian textiles and its impact on religious, social and economic scenario.
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They emphasized on the prerequisite of knowledge of chemistry, cultural requirements and

resource management for effective utilization of several other possible sources of Al-
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hyperaccumulating plants in addition to traditionally used plants. Recently Vankar et al.

(2008d) observed that Euriya acuminata when used as mordant in conjunction with Rubia
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cordifolia dye was found to enhance the dyeability of silk fabric by chelation due to the high
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Al content present in their leaves. In another study Cu-hyperaccumulating plant Pyrus pashia

have been reported to provide better dye adherence due to stronger and useful chelation to the

flavone/flavonol dyes extracted from Delonix regia (Vankar et al., 2009). Use of metal

hyperaccumulating plants as natural source of metal mordants is very promising concept

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which should be popularized as an alternate method that may help to reduce the reliance on

toxic metal salt mordants.

2.2. Enzyme assisted dyeing

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The use of enzymes in textile industry is an example of industrial biotechnology, which

allows the development of environment friendly technologies in fibre processing and

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strategies to improve the quality of final product. Different types of enzymes are commonly

used in various stages of textile processing for modification of physical and chemical surface

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properties or introduction of functional groups on the surface of textile fibres (Duran and

Duran, 2000; Jo et al., 2008). Many different approaches have been taken to the preparation,

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dyeing and finishing of cotton (Vankar and Shanker, 2008), wool (Montazer et al., 2009), silk
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(Vankar et al., 2007b; Vankar and Shanker 2009) and other textile fibres (Sricharussin, 2009)

with natural colorants using different types of enzymes. Tsatsaroni and co-authors used -
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amylase, amyloglycosidase and trypsin enzymes for preparation of cotton and wool samples
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for dyeing with saffron and curcumin (Kyriakides et al., 1998; Tsatsaroni et al., 1998). They
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have reported that enzymatic treatment resulted in improvement in dye uptake in all cases,

and attributed it to enhanced shrink-resistance properties of the treated fibres. Kumbasar et al.
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(2009) studied effects of alkali proteases on dyeing properties of various proteinous materials

with hydrolysable tannin based natural dyes obtained from sumac, myrobalan fruit, oak bark
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and gall nut and reported significant increase in dye uptake after enzymatic treatment.
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Madder dyed wool fabrics treated with protease (Parvinzadeh, 2007) and laccase (Montazer

et al., 2009) have shown higher water drop absorption, lower felting shrinkage, reduced

fabric weight and lower values of a*, b* and lightness without any change in fastness

properties of dyed samples. Vankar and co-authors studied effect of three enzymes lipase,

diasterase, proteaseamylase on dyeing characteristics of Terminalia arjuna, Punica

granatum, Rheum emodi (Vankar et al., 2007b), Acacia catechu, Tectona grandis and

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Delonix regia (Vankar and Shanker, 2008, 2009) on different types of textile fabrics. The

authors observed that enzymatic treatment gives rapid dye adsorption kinetics and total

higher adsorption than untreated samples in all the cases. The CIELab values also showed

improvement by enzymatic treatment. They showed that dye enzyme compatibility is an

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important factor in enhancing dyeing properties: protease-amylase combination is suited for

Acacia and Terminalia; lipase is suited for Rheum and Delonix, while diasterase is suited for

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Tectona and Punica. Compared to untreated wool, treatments with protease and

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transglutaminase enhanced K/S value of wool dyed with sappan dye; however no significant

changes were observed in fastness characteristics (Zhang and Cai, 2011).

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Although studies of enzymes used in natural textile dyeing (Table 3) have received limited

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attention in scientific literature, however, from the point of view of processing improvement,

quality enhancement of processed products, increased resource consumption and reduced

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environmental impacts by enzymatic dyeing induced the search for more industrial enzymes.

The latest development concerning advances in enzymatic application techniques provide

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possibilities for the development of new enzyme-based natural dyeing systems for a more
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eco-friendly approach in the textile industry, however further in depth research is needed

regarding dye enzyme compatibility for the choice of enzyme with a particular dye in order to
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adopt enzyme assisted dyeing method on commercial scale.

2.3. Sonicator-assisted dyeing

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The application of ultrasound power to textile dyeing has a significant role in the concept of

clean technology for textile processing. Ultrasound can improve effectiveness of a wide

variety of chemical and physical processes, mainly by generating cavitation in liquid medium

in addition to other mechanical effects such as dispersion, degassing, diffusion, and intense

agitation of liquid (Ahmed and El-Shishtawy, 2010). Cavitation is the formation, growth, and

implosive collapse of small gas bubbles caused by ultrasonically induced alternating

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compression and rarefaction waves. The cavitation bubbles oscillate and implode, thus

enhancing molecular motion and stirring effect in the dye bath. When cavitation occurs at a

solid/liquid interface (e.g., a fibre/dyebath interface), the resulting asymmetric implosion

produces micro streaming towards the solid surface which greatly disrupts the diffusion

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interlayer and promotes mass transport in that direction (Vankar et al., 2008a,b). Cavitation

and its physicochemical consequences enhance the dyeing rate; economize energy and time

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consumption without causing any apparent fibre damage (Vankar and Shanker, 2008). In the

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last few years a certain number of studies on ultrasound assisted natural dyeing and finishing

of natural and synthetic fibres were carried out at the experimental level. Ultrasonic energy

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provided easy efficient route for dye extraction, mordanting, and dyeing processes in

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comparison with the traditional methods (Mansour and Heffernan, 2011).

Kamel et al. (2005, 2007, 2009a, 2009b) comparatively investigated various parameters for
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dyeing of wool and cotton using ultrasound as well as conventional heating method and

reported that ultrasonic power substantially enhanced both dye (lac, cochineal and saffron)
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extractability and dyeability of fibres in comparison with conventional heating as a result of

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ultrasonic cavitation effect. Vankar and co-workers discussed the effectiveness of ultrasound

technology for dyeing of different type of textile fibres with commercially available natural
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dyes such as catechu, tectona (Vankar and Shanker, 2008), madder (Vankar et al., 2008d) and

identification, extraction and application of natural dyes from new vegetable sources such as
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Ixora coccinea (Vankar and Shanker, 2006), Eclipta alba (Vankar et al., 2007a), Symplocos
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spicata (Vankar et al.,2008a), Acer pectinatum (Vankar et al.,2008b), Mahonia napaulensis

(Vankar et al.,2008c), Delonix regia (Vankar and Shanker, 2009), Daphne papyraceae

(Vankar et al., 2009a), Melastoma malabathricum (Vankar et al., 2009b). Results obtained by

them in a series of experiments have shown superiority of sonicator dyeing over conventional

dyeing in terms of enhanced resource productivity, reduced wastes, reduced concentration of

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dyes and electrolytes in dyeing-bath and effluent along with significant increase in dyeing

performance and color characteristics of dyed fabrics without ignoring the stability conditions

of dye molecule. Xinsheng et al. (2008) reported the merits of ultrasonic extraction of dye

from Sargentodoxa cuneata and its application on wool fabric. The use of ultrasonic energy

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in dyeing woollen fabric in presence of glucose/hydrogen peroxide based redox system in

combination with alum mordant (Mansour, 2010) and silk fabric using mild mordants

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(Mansour and Heffernan, 2011) is found to have a significant improvement in dye uptake

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representing sonication efficiency in textile dyeing. Sivakumar et al. (2009, 2011) studied

extraction of colorants from some dye yielding plants such as beet roots, Green wattle barks,

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Marigold flowers, Pomegranate rinds, 4O clock plant flowers and Cocks comb flowers and

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reported significant improvement in extraction efficiency of the colorants due to the use of

ultrasound. Guesmi et al. (2013) reported substantial improvement of about 49.62% more dye
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uptake in case of sonicator dyeing of modified acrylic fabrics with indicaxanthin natural dye

in addition to better light, washing and water fastness results than the conventional method.
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The use of ultrasonics in natural textile dyeing provides the following benefits:
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Energy savings by dyeing at lower temperatures and reduced processing times,

Reduces pollution load by reduced consumption of auxiliary chemicals and increased

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dye exhaustion levels,

Improves processing efficiency and yield better product quality by allowing real-time
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control of color shade,

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Minimize damage to fibres during dyeing,

Lowers overall processing costs, thereby increasing industry competitiveness.

Use of sonication method for textile dyeing on commercial scale is definitely a cleaner

production strategy that offers an environmentally benign alternative to traditional exhaustion

method. As a general conclusion it could be said that replacing conventional thermal dyeing

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method with sonication method could make the process highly efficient, energy saving,

economical and low waste generation technique.

2.4. Other Chemical and radiation pre- and post- treatments

Recent developments in natural textile dyeing mainly rely on the modification of natural and

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synthetic fibres using various pre- and post-treatment agents for improvement in color,

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fastness and functional characteristics of dyed fabrics along with the focus on environmental

compatibility of these modification methods. Effect of various surface modification agents

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containing cationic (Kim et al., 2004; Kim and Park, 2007) and anionic groups (Kamel et al.,

2009a, 2011; Bulut and Akar, 2012) on dyeing properties of fabrics with different types of

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natural dyes have been evaluated frequently. Results indicated that pre-treatment of different

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types of fabrics with cationic and anionic agents enhances color strength and fastness

properties of dyeings over untreated dyeings to a significant extent. Fibre surface

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modification by the use of synthetic and natural polymers is also employed successfully for

enhancing absorption capacity naturally dyed fibers (Janhom et al., 2004, 2006). In recent
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years, a number of investigations have been carried out to exploit potential applicability of
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chitosan, a naturally occurring biopolymer with distinct chemical and biological properties,

as surface modification agent to improve dyeing performance and biofunctionalisation of

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cotton (Kavitha et al., 2007; Kim, 2006) and wool fabrics (Dev et al., 2009). The pre-

treatment of fabrics with chitosan increased the binding sites for the dyes resulting in better
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dye absorption (Chairat et al., 2011).

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Recently, dry modification processes such as sputtering and low temperature plasma (LPT)

treatment techniques that generate no waste have been introduced for the pretreatment and

finishing of textile fabrics as environment friendly alternative to wet chemical applications

(Ghoranneviss et al., 2011; Shahidi and Ghoranneviss; 2011). Plasma treatment of fibers

improves surface characteristics of fibers while the bulk properties of the fibers are not

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affected (Barani and Maleki, 2011). Wakida et al. (1998) marked the associated benefits of

oxygen, carbon tetrafluoride, and ammonia low temperature plasma treatments of wool and

nylon 6 fabrics for dyeing with several natural dyes, such as cochineal, Chinese cork tree,

madder, and gromwell. Park et al. (2008) subjected PET fabrics to chitosan and/or O2 low-

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temperature plasma as a pre-mordant in which the fabric was processed by padding, plasma-

etching, and immersion procedure and dyed with natural dye of Caesalpinia sappan. They

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showed that pre-treatment of PET fabrics with chitosan and/or plasma is better than a metal

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mordant in terms of the dye uptake and reduction in dyeing time. Surface pre-activation using

air atmospheric plasma and ultraviolet excimer treatment have also been used to activate PET

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fibrous surfaces yielding hydrophilic species, thereby increasing dyeing affinity with

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curcumin natural dye (Kerkeni et al., 2012). Chemical modification of cotton fabric with

reactive cyclodextrin (R-CD) at different concentrations resulted in remarkable enhancement

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in printability of cotton fabric as well as color strength of printed sample; however there was

no remarkable difference between fastness properties of modified and unmodified samples

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(Hebeish et al., 2006).

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The inherent poor light fastness of several natural dyes is a property which limits their use in

modern day applications. The use of UV absorbers and antioxidants are reported to have
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positive effect on the light fastness of naturally dyed fabrics (Cristea and Vilarem, 2006; Lee

et al., 2001). Introduction of a singlet oxygen quenching group into an ultraviolet absorber
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prepared as a means of improving the light fastness of naturally dyed fabrics provide a novel
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approach for improving the photostability of natural dyes (Oda, 2012a, 2012b). The

photostability of an anionic natural dye can be improved by intercalation into the hydrotalcite

layer, if the dye has a hydrophilic nature and a rather planar structure. The intercalated dye is

stabilized by the protection from the attack of the atmospheric oxygen (Kohno et al., 2009).

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Hydrophobic acrylic fibers pose a big problem for dyers due to their hydrophobic nature.

Incorporation of amino groups to acrylic fabrics by treatment with hydroxylamine

hydrochloride is reported to increase substantively of the fiber towards some anionic natural

dyes (Guesmi et al., 2012a, 2013). Modified acrylic fiber containing different amounts of

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amidoxime groups showed better dye uptake along with significant improvement in color

characteristics (El-Shishtawy et al., 2009). Considering pH sensitivity of natural dyes some

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researchers implied ammonia after treatment as useful technique to obtain better shades with

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improved colorimetric properties (Montazer et al., 2004; Montazer and Parvinzadeh 2004).

The preliminary studies on natural dyesurfactant interactions have shown that dyeing of

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fibres with the natural dyes in the presence of the surfactants enables good shade and fastness

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in color at low temperatures to be achieved and may minimize the damage to fibres during

dyeings (Chandravanshi and Upadhyay, 2012). Use of high energy radiations such as UV
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(Adeel et al., 2012; Iqbal et al., 2008) and gamma radiation (Bhatti et al., 2010; MGarrech

and Ncib, 2009; Naz et al., 2011) had also been reported to be beneficial in improving the dye
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uptake and color characteristics of naturally dyed fabrics.

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Pretreatment and finishing of textile fabrics by modern surface modification techniques, such

as use of eco-friendly biopolymers, plasma and radiation treatment technologies, relate to

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environmentally clean textile processing methodology and are much superior to traditional

chemical modification methods. Increasing momentum of advanced technologies in

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sustaining green chemistry aspects of processing and application shows that there is a
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significant potential to reduce the ecological impact of existing processes with the

introduction of these new concepts in real time methodologies of textile dyeing and finishing

focusing on realizing higher productivity gains in consumption of natural dyes without

compromising with eco-safety standards.

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2.5. Environmental and Socio-economic sustainability aspects of Natural Textile Dyeing

In recent years, both researchers and practitioners have devoted attention to environmental

and socio-economic sustainability issues in the textile industry (Thiry et al., 2011; Caniato,

2012). Despite the industrial relevance of the issue, structured analysis of the perspectives

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relevant to socio-economic and environmental impacts is severely missing in the literature

available on natural dyes. It is one of the biggest impeding factors in industrial utilization of

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natural dyes in modern textile industry. Since natural dyeing does not exist on a commercial

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scale in modern textile industry, currently most of the studies are based on laboratory results

or model processes. However, some discrete group of researchers have investigated the

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ecological position, future demands and availability of raw material, the handling, products

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properties, renewability and standardization for large scale production of natural dyes,

leveraging on environmental and economic sustainability to reach out to new market niches
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(Bechtold et al., 2003; Bechtold and Mahmud-Ali, 2008).

Basically, main sources of natural dyes can be divided in three categories:

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1. Primary products from agriculture

2. Waste and by products from farming and forestry

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3. Wastes from the food and beverage industries

Most of these studies available on natural dye sources and dyestuff extraction centered on
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collecting plant materials from wild and exploring the coloring properties of extracts from
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different plant parts. However, direct commercial use of native plants in dyestuff production

without investigating sustainability issues seems impractical and will lead to overexploitation

of natural resources. Studies focusing on agronomic potential and related environmental

consequences critical to harvesting natural dye yielding crops are rare. Indigo, madder, and

weld are some well screened natural dye crops which can be profitably harvested for

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industrial application (Gilbert and Cooke, 2001). There is need for economic valuation and

environmental monitoring studies that explicitly focus on potential natural dye crops that are

not commercialized, but rather harvested and consumed directly by indigenous households

(MacFoy, 2004; Dogan, 2003; Siva, 2007). Standerdized collection of this type of

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information from local inhabitants of different parts of world on indigenous natural dye

sources that can be harvested in that particular climatic condition is a first step in assuring

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environmental and socio-economic reality. Furthermore, for the commercial exploitation, the

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selected species must also be screened for their appropriateness in purview of modern

sustainable cultivation techniques.

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It is well know that the industrial system is very wasteful of materials and recycles very little

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(Ayres, 2004). Industrial sectors are experiencing the challenges of building up new systems

which have the capacity to recycle or reuse theses waste materials at minimal cost leading to
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the fulfillment of economic development and environmental sustainability objectives. The

idea of zero emission based on the notion that every biological waste is food for some other
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organism leads to the idea that some industry can always be found to consume another
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industrys wastes, although not always true, is very reasonable in natural dye production

from industrial wastes. Use of cheap by products from agriculture and forestry such as bark
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from timber industry e.g. Ash tree bark (Bechtold et al., 2007a), and leaves from abundantly

available palnts such as teak (Prusty et al., 2010), eucalyptus (Mongkholrattanasit, 2010), is
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a promising concept which can lower costs involved in natural dye production. Industrial
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food and beverage production produces huge amount of coloured plant wastes such as

pressed berries and distillation residues (Bechtold et al., 2006), pomace (Bechtold, 2007b),

peels (Sinha et al., 2012), shell (Ismal and Yildirim, 2012), and other residual by products

(Meksii et al., 2012) containing considerable quanitities of coloring matters which can be

utilized as promising source of natural dyes for textile industries after some careful

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investigation of supply chain system and optimization of processing variables (Bechtold and

Mahmud-Ali, 2008; Bechtold et al., 2009). Olive mill wastewater (OMW), (a by product of

olive extraction industry responsible for serious environmental concerns in Medditerranean

countries, as around 30 million m3 of OMW produced annually in this region) can be used as

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prospective source of natural coloring substances in olive oil producing countries which are

renewable, available in high quanitities and free costs (Meksi et al., 2012). An intensified use

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of industrial waste as renewable raw material for natural dye production represent

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sustainable cleaner production strategy as in addition to minimizing waste production and

conservation of fossil fuels, it would maximize economical use of waste materials.

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Production cost of natural dyes from direct harvesting are high as compared to production

AN
costs from waste and by-products. However, colours provided by agricultural primary

production could not be obtained with residues. Thus, any industrial natural dye production
M
unit must include both direct agricultural as well as residual sources for obtaining a complete

color pallete. Strategic combination of different plant sources allows the minimization of
D

cost to certain extent, and the average production cost of total color portfolio could be within
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the range of synthetic colorants (Geissler, 2009). Thrusting on minimizing the chemical load

of extraction procedure, Bechtold and coworkers suggested explicit use of water solvent in
EP

extraction of natural dyes from different sources (Bechtold et al., 2003, 2006; Bechtold and

Mahmud-Ali 2008). The use of other solvents may lead to highly contaminated waste water
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and plant residue, which require complicated aftertreatments leading to additional costs from
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solvent and chemical consumption and expensive deposition of contaminated wastes. They

also suggested combined dyestuff extraction and subsequent dyeing, as it will reduce

transportation cost and energy requirements of the process. Low exhaustion rates of natural

dyeing process is of great concern: firstly, it increases cost of dyeing process as unfixed dye

is not available for the coloration process and secondly, the dye present in the wastewater

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has to be removed in order to fulfill legal limits for textile effluents (Mussak and Bechtold,

2009).

Use of sonication in extraction and dyeing process presents a probable alternative to

traditional thermal exhaustion method of natural dyeing, as it increases dye exhaustion to a

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greater extent thus decrease the effleuent load and cost of natural dyeing (Sivakumar et al.,

2009; Mansour and Heffernan, 2011). Research findings on using enzyme as fabric pre-

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treatment method offers a cost effective and environmentally favorable soft chemistry

SC
option as enzymes are specific and fast in action and small amounts of enzyme often save

large amounts of raw materials, chemicals, energy and water (Vankar and Shanker, 2008;

U
Montazer et al., 2009). Another interesting aspect is reusing spent dye liquor in repeated

AN
dyeing cycles (Vankar et al., 2007b). Economic analysis as done by Shams-Nateri (2011) on

reusing waste water for wool dyeing with madder caused 19.91% cost saving.
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Huge amount of biomaterials are required for large scale production of natural dyes. Because

of low dye content of natural dye yielding plants, large amount of waste generated after
D

natural dye extraction creates an additional burden of waste disposal. Vankar et al. (2011)
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presented a very interesting study on biosorption efficacy of waste pulp generated after

natural dye extraction from some selected biomaterials (Canna indica flower, Portulaca
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olecera flower and stem, Hibiscus rosa sinensis flower and Trapa natans fruit skin) as an

alternative use other than just composting it. The demaonstrated that use of natural dye waste
C

as heavy metal adsorbents can be very effective in remediation of groundwater and surface
AC

water of chrome metals in contaminated sites of tannery operations.

It is undeniable that natural dyes are only used in a small scale by craftspersons, hobbyist

and indigenous people, and hardly used in modern textile industry. However, the emerging

body of literature on the environmental and economic issues of natural textile dyeing

demonstrates that, as the environmental impact is reduced throughout the whole life cycle

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(Fig. 2), the use of natural colorants is expected to contribute to sustainable development in

the near future (Ganglberger, 2009).

3. Natural dyes in functional finishing of textiles

The role of the textile finisher has become increasingly demanding, and now requires a

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careful balance between compatibility of different finishing products and treatments and the

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application processes used to provide textiles with desirable properties. Consumers

worldwide are looking for clothing and other textile products which provide greater comfort

SC
and remain fresh, hygienic and odor free in use. Investigation for innovative methods, for

development of hygienic textile products, in textile finishing processes and existing

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applications and problems in this area is the need of the hour. A number of reports are now

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available on natural colorants for imparting multifunctional properties to textiles such as

antimicrobial (Singh et al., 2005), insect repellent (Kato et al., 2004), deodorizing (Hwang et
M
al., 2008; Lee et al., 2008) and UV protective (Sarkar, 2004) properties. Chemical

constituents of some important natural dyes used in functional finishing of textiles are given
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in Fig. 3.
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3.1. Antimicrobial finishing

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Textiles have long been recognized as a media to support the growth of microbes as they

provide excellent environment for microbial growth and proliferation. Microbial growth on
C

textiles during use and storage imposes a number of undesirable effects for the textiles as
AC

well as users. These effects include generation of foul odors, discoloration, mildew

formation, apparel degradation, dermal infection, allergic responses and other related

diseases. A variety of synthetic antimicrobial textile agents have been reported such as

organometallics, phenols, organo silicones, quaternary ammonium compounds, N-halamines,

chitosan, polybiguanides, triclosan, nanoparticles of noble metals and metal oxides, and

bioactive plant-based products (Gao and Cranston, 2008; Simoncic and Tomsic, 2010). Most

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of them are complex in nature and take long time to complete their natural cycles and return

to nature. The challenges faced by textile finishing industry have intensified because of the

potential environmental risks and health and safety concerns emerging from use of synthetic

antimicrobial agents. There has been a growing need to develop eco-safe functional finishing

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agents for making textile products that can offer improved protection to the users from

microbes (bacteria, mould or fungi) by preventing the growth of microorganisms on fabrics

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used in wide range of clothing, home furnishings, commercial and industrial products (Gupta

SC
and Bhaumik, 2007; Ramchandran et al., 2004). With the steady increase in number of safe

and durable antimicrobial agents and textile finishing techniques, bioactive textiles are easily

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finding a place in the global textile market. Recent developments in bioactive agents of

AN
natural origin have opened new avenues in this area of research (Joshi et al., 2009).

Therapeutic properties of a number of dye yielding plants is well know and some of these
M
have been shown to posses significant antimicrobial effect (Calis et al., 2009; Gupta et al.,

2005; Lee et al, 2009). The antimicrobial activity of some of these dyes is reported as potent
D

owing to the existence of tannins (Prabhu and Teli, 2011; Shahid et al., 2012), flavonoids
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(Cushnie and Lamb, 2005), curcuminoids (Han and Yang, 2005), alkaloids (Kim and Son,

2005), and quinones (Khan et al., 2012) in their extracts. During last few decades, many non-
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toxic natural products have been tested for antimicrobial activity after application on wool,

cotton and other textile material with good results (Joshi et al., 2009).
C

Gupta and co-workers have studied antimicrobial properties of eleven commercially available
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natural dyes against some pathogenic gram positive and gram negative bacteria (Gupta et al.,

2004, 2005; Gupta and Laha, 2007; Singh et al., 2005). Antimicrobial activities of these dyes

are dependent on chemical structure and functional groups present in dye molecules. The

authors reported that tannin based natural dyes were most effective in inhibiting microbial

growth. They also ascertained that antimicrobial activity of a dye would vary when it is

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present in solution form than when it is held intimately to the textile substrate. Han and Yang

(2005) studied antimicrobial effect of curcumin (a yellow florescent pigment of carotenoid

class) after application on wool fabrics and established a quantitative relation between the

inhibition rate, curcumin concentrations and K/S values of treated woollen fabrics. Based on

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these relations, antimicrobial activity of wool fabrics finished with curcumin can be predicted

on the strains of S. aureus and E. coli without antimicrobial testing. Berberine, a natural

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cationic colorant was successfully employed onto cotton (Kim and Son, 2005), wool (Ke et

SC
al., 2006) and nylon (Son et al., 2007) to produce yellow colored fabrics with excellent

antimicrobial activity. Ammayappan and Moses (2009) used Aloe-vera, chitosan and

U
curcumin each separately as well as in different combinations to impart antimicrobial activity

AN
to cotton, wool and rabbit hair substrates. They revealed that peroxide treated cotton and

formic acid treated wool/rabbit hair substrates shows better antimicrobial activity than
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corresponding intact ones. Antimicrobial tests conducted on natural dyes obtained from

different plant waste materials such as waste leaves and superficial barks of Terminalia
D

catappa, Artocarpus heterophyllus, Tectona grandis, Morinda citrifolia (Prusty et al., 2010),
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Albizia lebbek and Saraca asoca (Baliarsingh et al., 2012) demonstrate an exciting

opportunity for producing naturally dyed silk yarn as a potential sustainable technique
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towards waste utilization and development of protective clothing. Ibrahim et al. (2010)

investigated various factors affecting dyeing and multifunctional properties of knitted cotton
C

fabric such as fabric structure, type and concentration of mordants, kind and percent of
AC

natural dye extract and dyeing procedure. They reported that susceptibility of tested microbes

to killing as they contact the surface of dyed samples are in order as G+ve > G-ve; most

probably due to the fact that G+ve bacterial cell wall consists of a single layer whereas G-ve

cell wall is multilayered bounded by outer cell membrane. Reports on effect of different

metallic salt mordants on antibacterial and antifungal activity of woollen yarns dyed with

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Acacia catechu (Khan et al., 2011), Lawsonia inermis (Yusuf et al., 2011, 2012), Rheum

emodi (Khan et al., 2012) and Quercus infectoria (Shahid et al., 2012) extracts showed that

mordanting with metallic salts decreased the antimicrobial activity of dyed yarns to some

extent, however durability of antimicrobial activity increased manifold. This could be the

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consequence of complex forming ability of metal salts with active functional groups of dye.

Some pigment producing fungi are also reported as potent sources of natural colorants which

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can be applied as antimicrobial finishing agents on silk (Saranya et al. 2012), cotton and

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leather (Velmurugan et al., 2009). Use of biomordants in place of metallic salt mordants is

found quiet helpful in enhancing antimicrobial activity of naturally dyed textile fabrics

U
(Prabhu et al., 2011, Prabhu and Teli, 2011). Few recent reports pointed out the use of

AN
modern innovative methods such plasma treatment (Chen and Chang, 2007; Ghoranneviss et

al., 2011), chitosan treatment (Dev et al., 2009), enzymatic treatment (Raja and Thilagavathi,
M
2011), cationization (Hong et al., 2012), microencapsulation and cross-linking

(Sathiyanarayanan et al., 2010) methods for enhancement in antimicrobial activity of

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naturally dyed textile materials. These innovative methods proved of immense help in
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improving bioactive properties of finished products.

Although, several efforts have been made to exploit various natural dyes for antimicrobial
EP

finishing of textiles, but still there is scarcity of systematic and logical approach for

implementation of these findings in real market of protective antimicrobial textiles. There are
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several key issues which are still remaining to be looked into. The major challenge in
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establishment of natural dyes as textile antimicrobial agents is the procurement of these

products in bulk quantities; and standardization of their extraction, purification and

application methods as the activity and composition of natural dyes obtained from same

source varies depending on their geographical location, method of extraction and application.

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Durability of finishing is a major concern to textile researcher and users since the finished

products are subjected to frequent laundering. Emphasis should be paid on the durability of

the treatment during conditions of subsequent storage and use, such as the rubbing, washing

and light exposure. The findings reported in cited literature demonstrate an exciting

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opportunity for the naturally dyed textile as a potential perspective in developing protective

clothing and other textile products for various application fields.

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3.2. UV-protective finishing

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Ultraviolet radiation (UVR) from the sun causes sunburns, tanning, premature skin aging and

wrinkling and its overexposure leads to skin cancer (Narayanan et al., 2010). Lifestyle

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changes such as excessive exposure to sunlight during leisure activities have increase chances

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of skin cancer. Exposure to the sun is an occupational hazard to outdoor workers such as

construction industry workers, recreation workers, sportspersons, agricultural and

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horticultural workers, and fishermen as they have no choice about the duration of their

exposure to sunlight. This necessitates the development of UV protective clothing and

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coverings to minimize the effect of harmful Ultraviolet radiation. UVR transmission

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properties of textiles are influence by many factors such as structure and physiochemical

nature of fibre, dyes and finishes, fabric thickness, porosity and moisture content (Gies, 2007;
EP

Sarkar, 2007). Fabric color also has a fundamental importance in UV protection (Grifoni et

al., 2009). The sun rays blocking properties of a textile are enhanced when a dye, pigment,
C

delustrants, or ultraviolet absorber finish is present that absorbs ultraviolet radiation and
AC

blocks its transmission through a fabric to the skin; thus dyed fabrics protect more than

undyed ones and their protection levels rise with the increase in dye concentration (Hustvedt

and Crews, 2005).

Sarkar (2004) characterized Ultraviolet Protection Factor (UPF) of plain, twill or sateen

weave cotton fabrics dyed with colorants of plant (madder and indigo) and insect (cochineal)

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origins with respect to fabric construction, weight, thickness and thread count. A positive

correlation exists between the weight, thickness and shade depth of the naturally dyed fabric

and their UPF values; however thread count appears to negatively correlate with UPF.

Feng et al. (2007) in an experiment conducted to evaluate UV protection properties of two

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natural dyes (Rheum and Lithospermum erythrorhizon) applied on cotton and silk found that

these natural dyes exhibit a comparable UV-absorption performance to benzophenone.

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Results demonstrated that UV-protective effect was strongly dependent on absorption

SC
characteristics of natural dyes for UVR. Grifoni et al. (2009, 2011) studied the effect of color

on UVR transmission of cotton, flax, hemp and ramie fabrics with different construction

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parameters dyed with some common natural dyes by in vitro and outdoor assessments. The

AN
comparison between two methods applied to measure fabric transmittance pointed out that

the UPFs calculated by in vitro measurements were generally lower than those based on
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outdoor data, indicating an underestimation of actual protection level of tested fabrics

assessed by in vitro test. Metallic salt mordants have been reported to enhance UV-protective
D

properties of naturally dyed cotton (Gupta et al., 2005), wool (Mongkholrattanasit et al.,
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2011a) and silk (Mongkholrattanasit et al., 2011b; Wang et al., 2009) fabrics to a substantial

account depending on nature of fibre, mordant and natural dye used. Very recently, Hou et al.
EP

(2013) used natural dyes extracted from orange peel (OP), an abundant, cheap and readily

available agricultural byproduct, for producing highly durable UV protective wool fabrics.
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They reported that UPF value of OP treated wool fabric was six times higher than that of the
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wool fabric dyed with normal synthetic dyes with similar shade and depth of shade and even

after 30 home laundering cycles, the UPF value of the OP dyed wool was found 4 times

higher than wool dyed with synthetic dyes.

To avoid the health risks associated with UV exposure, the use of sunscreens and UV

protective clothing has gained popularity among masses. Textiles have been considered

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primary tool in shielding UV radiations. Measurements of their properties in blocking UV

exhibit enormous differences between fabrics due mainly to their structure, composition and

color. Textile industries see a promising future for UV protective fabrics, with the

environmental and energy conservation benefits, in developing high performance materials

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for the world market. Therefore, it is contemporary need to develop a proper treatment to

increase the UV protection property to fabrics. Promising research findings obtained from

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laboratory scale and outdoor experiments shows that naturally dyed fabrics with UV

SC
protective properties seem to have bright future after some rigorous research and

development.

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3.3. Insect repellent finishing

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Insect damage on textile products such as carpets, garments, upholstered furniture, blankets,

and priceless heirlooms is a serious problem faced during storage and results in significant
M
economic losses, especially in warehouses and showrooms. Even a small amount of fibre

eaten from a valuable suit or a rug can ruin its functional and/or aesthetic properties. Insect
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repellents that discourage insect damage in textile industry are in great demand. Kato et al.
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(2004) studied damage to wool fabrics dyed with ten different natural dyestuffs by the larvae

of varied carpet beetle, Anthrenus verbasci. Eight among the ten natural dyestuffs were found
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effective against A. verbasci and strength of their repellent effect in feeding preference test

was in the order of lac dye, gallnut, catechu, red cabbage, Cricula cocoon extract > cochineal,
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indigo, Amur cork tree extract. Park et al. (2005) studied in detail the insect resistance of
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eight naturally occurring quinones and flavonoid dyes after application to wool with five

mordanting agents by using laboratory-reared black carpet beetles. The anthraquinone dyes,

such as cochineal and madder, were found to be very effective in protecting wool fabric

against black carpet beetles. Madder resulted in lowest weight loss and the best effect of

insect deterrence against black carpet beetles.

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4. Natural dyes in Dye Sensitized Solar Cells (DSSC)

At present, we are mostly dependant on fossil fuels i.e. coal, crude oil and natural gas for our

energy needs. These fuels being non-renewable and limited in supply are constantly

exhausted, thus are creating a huge problem for the future generations. Therefore, a search for

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renewable low environmental impact alternative energy sources is considered one of the top

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priorities in today's society. Among renewable energy resources, solar energy is the largest

exploitable resource, which provides more energy in 1 hour to the earth than all of the energy

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consumed on the planet in one year (Lewis and Nocera, 2006).

A dye-sensitized solar cell (DSSC) (Fig. 4) is a third generation photovoltaic device for the

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conversion of visible light into electric energy which provides a technically and economically
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credible alternative concept to present day pn junction photovoltaic devices (Gratzel, 2003).

It has emerged as one of the promising renewable energy sources for eco-friendly and cost
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effective conversion of solar energy to electricity and due to the use of inexpensive materials,
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simple fabrication process and low environmental impact, especially those sensitized by
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natural dyes (Narayan, 2012; Patrocinio et al 2009). Dye-sensitized solar cells are innovative

solar cells that mimic photosynthesis in plants. Unlike traditional solar cells, dye-sensitized
EP

cells can work effectively in low light conditions and are less susceptible to losing energy to

heat. The efficiency of DSSC is determined mainly by the sensitizer used. The dye as a
C

sensitizer plays a key role in absorbing sunlight and transforming solar energy into electrical
AC

energy (Zhou et al., 2011). DSSCs with efficiencies of up to 11% have been designed using

ruthenium (Ru) based dyes but the limited availability and high cost of these dyes together

with their undesirable environmental impact have led to the search for cheaper and safer dyes

(Campbell et al., 2007).

There have been some interesting explorations of natural dyes in the context of the dye-

sensitized solar cell (DSSC) application using pigments obtained from biomaterials. Several

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reports have emphasized on exploration into natural dyes, such as cyanine (Sirimanne, 2006),

anthocyanins (Fernando and Senadeera 2008; Zhu et al, 2008), cyanidins (Senthil et al.,

2011), tannins (Espinosa et al., 2005), chlorophyll and their derivatives (Chang and Lo, 2010;

Calogero et al., 2009), carotenoids (Yamazaki et al, 2007), betalains (Calogero et al., 2012;

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Zhang et al., 2008), chalcones (Agarkar et al., 2011), and many others (Ito et al., 2010; Sang-

aroon et al., 2012) as a cheaper, faster, low-energy requiring and environment friendly

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alternative for use in dye sensitized solar cells. Although these natural dyes often work

SC
poorly in DSSCs, these are expected as low cost and prepared easily comparing to ruthenium

(Ru) complex based dyes.

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Different types of natural dyes showed different solar conversion efficiencies depending on

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the source and chemical structure of dye and interaction between dye molecule and photo

electrode i.e., TiO2, ZnO etc (Hao et al., 2006; Narayan, 2012; Thambidurai 2011; Zhou et
M
al., 2011). Natural dye sensitized DSSCs usually perform poorly in DSSC because of weak

binding energy with the metal oxide film (photo-electrode) and low charge-transfer
D

absorption in the whole visible range. Based on investigation on the structure and properties
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of dye molecules, the best photosensitized effect in the some of the tested natural dyes is

obtained due to the better interaction between the different binding groups of dye molecule
EP

on and the TiO2 film on cathode in DSSCs. Heera and Cindrella (2010) theoretically

evaluated ten natural pigments: caffeic acid, ferulic acid, ellagic acid, deoxysantalin,
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resveratrol (plant source), carminic acid, kersemic acid, ommatin D (insects), methoxatin and
AC

caulerpinic acid (microbes), as photosensitizers for their possible application in DSSC and

concluded that resveratrol, ferulic acid, caffeic acid and methoxatin can prove potential

pigments for efficient application in DSSC due to their favourable wavelength maximum

much compatible with TiO2 and their high oscillator strength. Gomez-Ortiz et al. (2010)

investigated the use of bixin and norbixin obtained from achiotes seeds in DSSCs based on

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TiO2 and ZnO substrates and confirmed that the efficiencies obtained with TiO2 are much

higher than for ZnO substrates, in agreement with the general trends observed for these two

substrate materials. Yamazaki et al. (2007) assembled DSSCs by using natural carotenoids,

crocetin and crocin, as sensitizers and demonstrated that, crocetin can attach effectively to the

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surface of TiO2 film due to the presence of carboxylic groups in the molecule and perform the

better photosensitization effect than crocin that has no carboxylic group in the molecule.

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Extracting temperature, extracting solvent and pH of the extract solution also have very

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prominent role in determining efficiency and stability of DSSCs (Chang et al., 2010;

Wongcharee et al, 2007).

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Meng et al. (2008) elucidated the electronic coupling between a TiO2 nanowire and a

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cyanidin natural dye sensitizer and provided insight into charge injection mechanisms of

natural-dye sensitized nanowire solar cells. By exploring various nanowire orientations and
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dye adsorption sites they showed that their system has additional advantages over traditional

DSSCs such as free availability of the dye, large surface area, environmentally benign
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components, and improved light scattering and charge transport, all of which contribute
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toward improving key characteristics, that is, low cost and high efficiency. DFT

characterization of the molecular properties of different natural pigments relevant to dye-

EP

sensitized solar cells for better understanding of the electron injection process is also reported

in literature (Qin and Clark, 2007; Sang-aroon et al., 2012).

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Several innovative methods have been developed for performance improvement of natural
AC

dye-sensitized solar cells. The incorporation of carbon nanotubes as counter electrode in

natural dye anthocyanin-sensitized solar cells can potentially improve the mechanical and

environmental stability of DSSCs in addition to enhancing their conversion efficiency (Zhu et

al., 2008). In another experiment overall conversion efficiencies of DSSCs fabricated with

natural sensitizers obtained from pomegranate juice for cells operated with Pt

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electrodeposited counter electrode were found much higher than carbon coated counter

electrode (Bazargan, 2010). Luo et al. (2009) assembled DSSCs by using electrophoresis

technique for fabrication of TiO2 film with natural dyes extracted from C. indica L., S.

splendens, cowberry and S. nigrum L. as sensitizers. Dai and Rabani (2001; 2002) employed

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anthocyanins extracted from pomegranate as aqueous mediators for DSSCs and studied the

effect of the mediator solvent in the performance of solar cells sensitized by commercially

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available anthocyanins. Sandquist and McHale (2011) explored the use of a blocking layer

SC
and treatment by TiCl4 in order to optimize the performance of the betanin-based dye-

sensitized solar cells, and recorded the highest energy conversion efficiencies as high as 2.7%

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for a DSSC containing a single unmodified natural dye sensitizer. In a combined

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experimental and theoretical study of natural betalain pigments Oprea et al. (2012) identified

betacyanins as the useful constituents of red beet root extract as natural sensitizers and
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emphasized on the role of extract purification for better results. Kumara et al., (2006)

investigated synergistic sensitization by dye cocktail (shishonin and chlorophyll) obtained

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from shiso leaves and successfully achieved broadening of spectral response of dye sensitized
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solar devices. Synergistic effect of mixed pigments in the energy transfer of the pigment

sensitized mesoporous TiO2 solar cells was further confirmed by experiments on DSSCs
EP

fabricated with mixed chlorophyll and xanthophylls pigments extracted from different plants

(Bao-Qi et al., 2008). Eenergy conversion efficiencies and maximum power output for solar
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cells sensitized by mixed pigments were much higher than that achieved by the linear
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superposition of the cells sensitized by individual pigments. Furukawa et al (2009) fabricated

various DSSCs using natural dyes of red cabbage, curcumin, red-perilla and their mixtures.

They found that the conversion efficiency of the solar cells fabricated using the mixture of

red cabbage and curcumin was much larger than that of solar cells using one kind of dye.

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They also reported that the cost performance of solar cells sensitized with red cabbage is

lower by more than 50 times than that of solar cells using Ruthenium complexes.

In a recent study, Park et al. (2013) observed that procedure of adsorbing the binary dye onto

TiO2 film is also a very important factor in determining the performance of fabricated cells.

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They reported that the energy conversion efficiency of the TiO2 electrode with successive

adsorptions of gardenia yellow (GY) and gardenia blue (GB) dyes was 0.59%, which is

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enhanced compared to single dye adsorption (0.32% for GY and 0.16% for GB), however

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adsorption of GY and GB dye mixture resulted in much lower energy conversion efficiency

(0.04%). The decrease in efficiency of such cocktail dyes due to unfavorable interactions

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between the two dyes.

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Incorporation of a natural dye sensitized solar cell fabrication module in conventional science

laboratory courses is an effective approach, which provides an interdisciplinary, practical

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model for students learning the basic principles of biological extraction, chemistry, physics,

environmental science, electron transfer and photochemical technology (Smestad and

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Graztel, 1998). Few researchers have taken into account the educational importance of
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naturally sensitized solar cells and presented their experiments as interesting

multidisciplinary exercises for dissemination of knowledge and to educate people on

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renewable energy resources (Calogero and Marco, 2008; Raturi and Fepuleai, 2010; Smestad

1998).
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Despite the effort involved the in use of natural dyes as sensitizers, low conversion
AC

efficiencies of these DSSCs would appear to be unpromising from a commercial viewpoint.

Although a number of natural dyes have been tested for their performance in DSSCs (Table

4), most of them yielded conversion efficiencies of less than 1%. Betanin extracted from beet

roots, =2.71% (Sandquist and McHale, 2011), Xanthomonascin-A extracted from Monacus

purpureus, =2.3% (Ito et al., 2010), and isobutrin from Butea monosperma, =1.8%

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(Agarkar et al., 2011) were found to be the best photosensitizers for use in DSSCs compared

with other natural dyes, except for some chlorophyll derivatives which yielded conversion

efficiencies over 2% (Calogero et al., 2009). Natural chlorophyll derivative chlorin-e6

exhibited energy conversion efficiencies over 4% (Ikegami et al., 2008). The efficiency of

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natural dye sensitized solar cells is determined by a number of factors that include selection

of the appropriate natural dye, quantitatively significant stable electronic anchorage of the

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dye to the surface of the metal oxide nanostructure, choice of photoanode, counter electrodes,

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electrolyte and solvent system. It is therefore highly desirable to standardize these critical

factors in the context of making natural dye sensitized solar cells a commercially viable

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option. The advantages of natural dyes as photosensitizers are large absorption coefficients,

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high light-harvesting efficiency, no resource limitations, low cost, simple preparation

techniques and no harm to the environment. Although the efficiencies obtained with these
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natural dyes are still below the current requirements for large scale practical applications,

these interesting explorations of fabrication of dye-sensitized solar cell using dyes obtained
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from bioresources invoked participation of researchers around the globe to engage in research
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to search for new sources of natural dye systems that are stable, nontoxic, biocompatible and

have desirable optoelectronic properties. Some serious efforts in natural dye sensitizers may
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spring up a perspective of commercial feasibility for inexpensive and environmentally

friendly Dye Sensitized Solar Cells.

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5. Natural dyes in food coloration

AC

As a consequence of growing worldwide concern for food quality and safety, a set of

standards have been brought in by different governments. Market pressure brought about by

changes in legislation and consumer preferences have necessitated the foods to be formulated

with more natural ingredients. The use of natural pigments for food coloring is receiving

growing interest from both food manufacturers as well as consumers and there has been much

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interest in development of new natural colorants for use in food industry in the continuing

replacement of synthetic food dyes because natural products are associated with quality and

health promotion whereas synthetic pigments are critically assessed by consumers (Dawson,

2008; Downham and Collins, 2000; Henry, 2000). Standardized methods of collection,

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extraction, purification, stabilization and standardization for a variety of natural food

colorants are available such as anthocyanins (Wrolstad, 2004), betalains (Azeredo, 2009; Roy

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et al., 2004; Stintzing and Carle, 2007), chlorophylls (Humphrey, 2004; Kong et al., 2012),

SC
carotenoids (Mortensen, 2006), tannins (Vankar et al., 2006), Monascus (Dufosse et al.,

2005), quinones (Gonzalez, 2002), biliproteins (Sekar and Chandramohan, 2008), safflower

U
(Cho et al., 2000), turmeric (Marcolino et al., 2011) etc. They have different groups of

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chemical compounds which may be used directly as colorants or in chemically modified form

to produce different hues ranging from green through yellow, orange, red, blue, and violet,
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depending on the source of colorant or increased stability (Bakowska-Barczak, 2005).

Researchers willing to experiment and expand this interesting palette of natural food color
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choices to give distinguished look and quality to a variety of food preparations.

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In most of the countries strict regulations have been formulated regarding the use of food

additives including colorants. Perhaps, every country has its own basic color additive
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regulations, and acceptable standards vary widely from one country to the other. With

dwindling number of approved synthetic colors over the years, researchers have devoted
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more attention to the development of natural food colors, as they are generally more
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internationally accepted (Burrows, 2009). Table 5 lists naturally derived colorants approved

by EU, USA and Japan for use in food coloring. Downham & Collins (2000) portrayed a very

illustrative picture of future outlook of legislation, innovations in formulation and processing

technologies for food colorants by taking backdrop of recent developments. They concluded

that the natural food color market will grow on a global scale at a faster rate than synthetic

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colors owing to a continued consumer pressure to `go natural'. The production of many

currently approved natural food colorants has a number of disadvantages including

dependence on supply of raw materials and variation in extracted pigments (Mapari et al.,

2005). A number of reports are available on exploitation of the potential of new sources of

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plants (Castellar et al., 2008; Longo and Vasapollo, 2005; Lin et al., 2010) and insect

(Gonzalez, 2002; Borges et al., 2012) origin as well as other biological sources such as fungi

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(Duran et al, 2002; Mapari et al, 2005; Velmurugan et al., 2010), bacteria (Zhang et al.,

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2006), and algae (Campo et al., 2007; Dufosse et al., 2005) in addition to those covered by

existing legislations. Most of the currently used natural pigments are highly sensitive to pH

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change, temperature and prone to light, heat and oxygen disintegration (Delgado-Vargas et

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al., 2000). Ascertaining the color stability of natural colorants as pre-requisite for their

successful application a number of researchers focused on improving color stability of

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different classes of natural food colorants (Castaeda-Ovando et al., 2009; Herbach et al.,

2006). Although, the wealth of information is now available on new sources for food
D

colorants, however, any new pigment source would require rigorous assessment of
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established safety tolerances and should meet the economic, legal and aesthetic requirements,

for approval by food regulatory authorities (Dowham and Collins, 2000).

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Pigments producing microbes such as fungi, bacteria and microalgae are quite common in

nature. Among the molecules produced are carotenoids, melanins, flavins, quinones and more
C

specifically monascins, violacein, phycocyanin or indigo (Dufosse, 2006). A great upsurge

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has been seen in recent times in biotechnological production of food grade pigments

(Chattopadhyay et al., 2008). A number of alternative biosynthetic methods are available for

the commercial production of natural colors using diverse microbial sources. With recent

advances in genetic engineering technology, attempts have been made to create microbial cell

factories for the production of food colorants through the heterologous expression of

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biosynthetic pathways from either already known or novel pigment producers (Dawson,

2009). The use of fungi to color foodstuffs is not new; Monascus pigments are being

traditionally used in food in the Orient for hundreds of years. Fungi provide a readily

available alternative source of naturally derived food colorants. The recent approval of a

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fungal food colorant has tremendously increased the prospects of research to explore the

extraordinary chemical diversity and biodiversity of fungi for the biotechnological production

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of pigments as natural food colorants. Recent data indicate that with an appropriate selection

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of suitable fungus using chemotaxonomic tools and a priori knowledge of fungal extrolites,

fungi can be used as cell factories for pigment production and could be developed to tailor

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functionality and expand the color palette of existing natural food colorants; the fungal

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natural colorants could be produced in high yields by using the available cultivation

technology without potential genetic manipulation since tougher legislation and skeptical
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attitude of consumers make it rather difficult for the acceptance of genetically modified food

(Mapari et al., 2005, 2006, 2009, 2010). Micro-algae are also seen as a major natural source
D

for a vast variety/array of natural colors. Campo et al. (2007) presented a beautiful picture of
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current state and future perspectives of carotenoid colorant production by microalgal

cultivation. Carotenoid production has been proved to be one of the most successful branches
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of biotechnology of microalgae.

Innumerable associated benefits and myriad therapeutic properties are linked with the use of
C

natural colorants in food industry (Chattopadhyay et al., 2008; Siva et al., 2011). For
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example, in addition to coloring property, anthocyanin extracts may act as quality control

marker for food stuffs; improve the nutritional quality of foods and beverages, possibly play

an important role in reducing the risk of coronary heart disease, cancer, and stroke (Wrolstad,

2004, 2005). Carotenes are also used for nutritional purposes an essential vitamin source

(provitamin A agents) or as dietary supplements (Mortensen, 2006). Paprika is a source of

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vitamin C, whereas riboflavin contains vitamin B (Burrows, 2009). Many of the natural food

colorants possess excellent antioxidant properties (Beutner et al., 2001). Flavonoids and

tannins are recognized as colorants with high pharmacological value (Chattopadhyay et al.,

2008). Thus, in addition to their primary function of improving the visual quality of food

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products, naturally derived food colorants may improve the nutritional value of the target

food. These prospective nutraceutical properties may play increasingly important role in

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making a choice between natural or syathetic food colors at a time, where human diet is more

SC
and more based on processed foods (Stintzing and Carle, 2007).

Appearance, consumer preferences and safety standards of foods and food colors coupled

U
with economics and application technology will always play a key role in the success of new

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food products. At one time, synthetic colors were the first choice as food colorants and

natural colorants were relegated to a limited number of traditional applications because of

M
limited availability, difficulty in use, instability and high cost. The renewed interest in natural

food coloration is resulted due to stringent regulatory pressure, bad publicity for the synthetic
D

food colors and need for globally approved colorants (Frick, 2003). With biotechnological
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advances, contemporary researchers are in a position to simplify the techniques for

production of the existing colorants and find new colorant sources for their
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commercialization. By appropriate selection of new sources for known colorants, formulating

new ways for existing pigments and improvement of existing sources by mutation or genetic
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engineering techniques better pigments production yield could be achieved. Although many
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advances in the developments of natural food colors covering different aspects such as

extraction, purification, stability, identification of new sources, formulation techniques as

well as related hygiene and safety criteria have been made over the last three decades there is

still a great scope for the discovery of relatively better and more stable natural pigments that

may have wider industrial applications.

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6. Other applications of natural dyes

In addition to above mentioned applications, there is a growing interest for using natural dyes

to dye leather (Sivakumar et al., 2009; Selvi et al., 2013); to stain wood (Goktas et al., 2008),

pulp (Savvidou and Economides, 2007), and some plastics (van den Oever, 2004); to add

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color to cosmetics (Kapoor, 2005; Kapoor et. al, 2008); to dye hair (Boonsong et al., 2012;

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Komboonchoo and Bechtold, 2009; Rao et al., 2008); to impart color to some pharmaceutical

preparations (Chigurupati, 2002); and also in histological staining (Tousson, and Al-

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Behbehani, 2011). Different prospects of natural colorants used in/as cosmetics products are

comprehensively reviewed by Dweck (2002, 2009a,b). Natural pigments derived from

U
different sources with active functional components have shown high biological activities,

AN
and exhibited different properties depending on each kind of pigments which makes them

excellent coloring materials for natural cosmetics and functional health foods (Boo et al.,
M
2012). van den Oever et al. (2004) studied the application of several food grade colorants for

use in coloration of thermoplastics and suggested some of best performing natural colorants
D

such as indigo and anthraquinone-based colorants can be used in appliances where moderate
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properties concerning heat resistance and (UV) light stability are required, such as indoor PP

applications and PVC water drainage pipes. Use of curcumin as sensitizer for
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photopolymerization of styrene is also reported (Mishra and Daswal, 2007). Siva et al. (2008)
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reported an easy, practical and reliable procedure for using Bixa orellana L. natural dye as an
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alternative tracking dye for gel electrophoresis in place of regularly used dye marker

bromophenol blue (BPB). Another very common aspect of natural dye application is their use

as pH indicator (Khan and Farooqui, 2011; Mishra et al., 2012; Ramamoorthy et al., 2009).

Shin et al., (2010) developed thermo-regulating natural indigo dyed fabrics through the

fixation of the Microcapsules (MCs) containing n-octadecane and n-eicosane on the back side

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of the fabrics using the dot-screen printing method. They obtained relatively good latent heat

storage capacity and color durability to rubbing, laundering, and ironing. Recently, Singh et

al. (2010) demonstrated the potential use of naturally derived vermillion and indigo dye in

Cheiloscopy (study of lip prints) for forensic applications. Anthocyanin based natural dyes

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are also tested as safe TiO2-sensitizer for photodergadation of organic contaminants in water

purification systems as a promising replacement for more costly and hazardous heavy metal

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based systems such as CdS particles and Ru-compounds (Zyoud et al., 2011). Kuswandi et al.

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(2012) employed curcumin natural dye as chemical sensors for detection of volatile inorganic

and organic amines produced during bacterial growth in shrimp samples. They showed that

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curcumin immobilized on bacterial cellulose membrane (biopolymers) can be used as a

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package sticker sensor for the visual detection of shrimp spoilage and could offer an extra

analytical device both to the fish industries and retailers who are interested in approaches and
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devices that are rapid, disposable, non-destructive, safe, low cost, simple, and with real time

applications. Sharma et al. (2012b) explored a new arena in the applicability of natural dyes
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isolated from R. emodi, revealing the use of dye as an extrinsic probe to determine the
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thermal stability of proteins by exploiting the fluorescence properties of anthraquinone

derivatives for their interactions with relevant target proteins.

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Researchers have lately explored the promise of some historical pigments such as indigo and

madder in designing novel organic electronics devices successfully. Recent explorations on

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thin films of indigo and Tyrain purple have shown their good charge transport properties for
AC

use in organic electronics as natural and sustainable semiconductors. Indigo and Tyrian

purple form highly ordered thin films that afford ambipolar charge transport with relatively

high mobilities. Inspiring results have shown that these biomaterials can compete with the

best organic electronic materials and in conjunction with other biomaterials (i.e. substrate,

dielectric) they demonstrate the possibility of creating fully biocompatible/biodegradable

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electronics for many low cost applications (Gowacki et al., 2012; Irimia-Vladu et al., 2012;

Robb et al., 2013). Reddy et al. (2012) reported reversible lithium ion storage properties of a

naturally occurring and abundant organic compound purpurin, a non-toxic dye derived from

widely available plant madder, to develop sustainable and eco-friendly lithium ion

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batteries. The lithium batteries assembled using purpurin and chemically lithiated purpurin

(CPL) as working electrode showed good charge/discharge characteristics with very good

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reversible lithium ion storage properties. Future largescale application of sustainable organic

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electronics based on biodegradable materials would have a positive impact on the current

problem of electronic waste.

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These interesting findings on newly discovered panoramas of natural dye applications invoke

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great expectations for further research on utilization of natural dyes in a wide variety of fields

with focus on the future industrial application.

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7. Conclusion
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Natural dyes, generally supposed to be cheap, nontoxic, renewable and sustainable resource
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with minimal environmental impact, have attracted the attention of the scientific community

to use them in a variety of traditional and newly discovered application disciplines. Although,
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past few years have witnessed substantial growth in our understanding of technological

details required for efficient utilization of colorants obtained from natural sources, but still
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there are a number of technical challenges in each area of natural dye application that must be
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overcome before these technologies can be adopted on a practical large scale. Improving

methodologies of extraction and application and generating cost-effective processes are

currently challenging because of the large diversity of natural dye sources. Enthusiastic

studies discussed in the present article assert that current incompatibility of commercial

exploitation of laboratory scale results can be carried off with some serious efforts. The data

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generated from these studies may device the basis for the economic viability of natural dye

production in commercial scale for sustainable utilization of bio-resources. Extensive R&D in

the area of natural dye applications is underway worldwide, but practical implementation to

adopt new technologies for making natural dyes a compatible co-partner with synthetic dyes

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in different spheres of our life is a long term prospect.

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Acknowledgement:

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Financial support provided by University Grant Commission, Govt. of India; through BSR

Research Fellowship in Science for Meritorious Students (Mohammad Shahid) and Research

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Fellowship to Central University Ph.D. Students (Shahid-ul-Islam) is thankfully

acknowledged.
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Table 1: List of metallic mordants used in natural textile dyeing

Mordants Chemical References

formula
Conventional metallic mordants
Alum KAl(SO4)212H2O Park et al., 2005; Samanta and Agarwal, 2009; Vankar et al., 2007a,

PT
Ferrous sulfate FeSO4.7H2O 2008a; Zarkogianni et al., 2011
Stannous chloride SnCl2.2H2O
Copper sulfate CuSO4.5H2O
Potassium dichromate K2Cr2O7

RI
Newly discovered metallic mordants

Magnesium sulphate MgSO4.7H2O Das et al., 2008; Moiz et al., 2010; Rekaby et al., 2009

SC
Aluminium sulphate Al2(SO4)3.13H2O Das et al., 2008; Hwang et al., 2008; Yi and Cho, 2008

Zinc sulphate ZnSO4.7H2O Ghouila et al., 2012; Guesmi et al., 2012a,b; Onal et al., 2005

Manganese sulphate MnSO4.5H2O Hwang et al., 2008; Lee et al., 2004

U
Nickel sulphate NiSO4.6H2O Hwang et al., 2008; Lee et al., 2004

Cobalt sulphate

Stannous sulphate
CoSO4.6H2O

SnSO4
AN Guesmi et al., 2012a,b; Hwang et al., 2008;

Hwang et al., 2008

M
Stannic chloride SnCl4.5H2O Vankar et al., 2007a, 2008a

Ferric chloride FeCl3 Mikropoulou et al., 2009; Rekaby et al., 2009; Zarkogianni et al., 2011

CuCl22H2O Ibrahim et al., 2010

D

Copper chloride

Zinc Chloride ZnCl2 Ibrahim et al., 2010; Zarkogianni et al., 2011

TE

Aluminum chloride AlCl36H2O Ibrahim et al., 2010

Aluminium nitrate Al(NO3)3. 9H2O Onal et al., 2005

EP

Calcium hydroxide Ca(OH)2 Chairat et al., 2007

Zinc tetrafluoroborate Zn(BF4)2 Chairat et al., 2007

Lanthanum Oxide La2O3 Wang et al., 2012

C

Rare earth chlorides

AC

Rhenium trichloride ReCl36H2O Zheng et al., 2011

Neodymium trichloride NdCl36H2O Zheng et al., 2011

Zirconium oxy chloride ZrOCl28H2O Ibrahim et al., 2010

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Table 2: List of plants used as source of biomordants in natural textile dyeing

Botanical Name Reason for use as References

mordant
Acacia catechu Used as sources of tannin Mansour and Heffernan, 2011
Emblica officinalis mordant Prabhu et al., 2011

PT
Entada spiralis Chairat et al., 2007
Eucalyptus Sachan and Kapoor, 2007
Memecylon scutellatum Chairat et al., 2011

RI
Punica granatum Chattopadhyay et al., 2013
Quercus infectoria Grifoni et al., 2011
Rhus coriaria Bruni et al., 2011

SC
Rumex Hymenosepolus Haji, 2010
Tamarindus indica Prabhu and Teli, 2011
Terminalia bellerica Shekhawat, 2012
Terminalia chebula Samanta et al., 2011

U
Prosopis spp. Shekhawat, 2012
Enterolobium cyclocarpum Arroyo-Figueroa et al., 2011
Caesalpinia coriaria

Symplococcus sp.
AN
Al-hyperaccumulating plants
Arroyo-Figueroa et al., 2011

Cunningham et al., 2011

Aporusa sp. used as substitute of alum Cunningham et al., 2011
M
Baccaurea racemosa mordant Cunningham et al., 2011
Xanthophyllum lanceatum Cunningham et al., 2011
Eurya acuminata Vankar et al, 2008d
D

Pyrus pashia Cu rich plant used as substitute Vankar and Shanker, 2009
of copper mordant
TE
C EP
AC

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Table 3: Enzymatic application in natural Textile dyeing

Reference Enzyme Substrate Treatment Conditions Natural Dyes used in the study

PT
Class Trade Name Source pH Temp. Treatment Time
(oC) (Min)
Raja and Protease - - Wool 9 70 60 Grevillea robusta, Spathodea
Thilagavathi, campnulata, Cassia auriculata, Acacia

RI
2011 decurrens
Zhang and Cai, Protease Savinase 16L - Wool 8 50 45 Caesalpinia sappan
2011

SC
Transglutaminase - - 7 50 40
Montazer et al., Laccase Denilite II S - Wool 4.5 60 60 Rubia tinctorum
2009
Parvinzadeh, Protease Novolan T Bacillus sp. Wool 7 30 60 Rubia tinctorum

U
2007
Kumbasar et al., Protease Savinase Bacillus licheniformis Wool and 9-9.5 50 20 Rhus coriaria, Terminalia chebula, Quercus

AN
2009 Silk alba, Quercus infactoria
Alcalase Bacillus amyloliquefaciens 8-8.5 60 20
Vankar et al., Protease - Aspergillus oryzae Cotton 7.2 25 10 Terminalia Arjuna, Punica granatum,
2006; Vankar and silk Rheum emodi, Acacia catechu, Tectona

M
Amylase - Aspergillus niger 7.1 30 10
and Shanker, 7.0 30 10
grandis, Delonix regia
Lipase - Aspergillus niger
2008, 2009
Diasterase - - 7.2 25 10

D
Kyriakides et Amylase - - Cotton 7 - 10 Crocus sativus, Curcuma longa
al., 1998; Trypsin - - TE and Wool 8 - 30
Tsatsaroni et
al., 1998
- Not specified
C EP
AC

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Table 4: Functional parameters of various natural dye sensitized solar cells

Dye Molecular structure Photoelectrode Counter Electrolyte composition Solvent system Jsc Voc FF Reference

PT
2
Electrode (mA/cm ) (V)

Red beet roots Betanin TiO2 caoted FTO Pt caoted FTO LiI/ I2/TBP 3-methoxyprpionitrile 2.42 0.44 0.63 0.67 Zhang et al., 2008
Betaxanthin Acetonitrile 2.00 0.22 0.51 0.19
Red cabbage:curcumin - TiO2 caoted FTO Pt coated ITO LiI/I2/DMPImI/TBP Propylene carbonate 0.81 0.53 0.69 0.60 Furukawa et al., 2009

RI
Red perilla Shisonin 0.39 0.51 0.67 0.27
Red cabbage - 0.56 1.55 0.67 1.17
Chaste tree fruit - TiO2 caoted FTO Pt caoted ITO LiI/I2 Acetonitrile/ 1.06 0.39 0.48 - Garcia et al., 2003
Morus alba - 3-methyl-2-oxazolidinone 0.86 0.422 0.43 -

SC
Euterpe oleraceaa - 0.37 0.442 0.61 -
Beta vulgaris rubra - TiO2 caoted FTO Pt caoted FTO LiI/ I2 3-methoxypropionitrile 9.5 0.425 0.35 1.7 Calogero et al., 2010
Opuntia engelmannii - 9.4 0.350 0.38 1.26
Opuntia ficus indica - 2.7 0.375 0.54 0.50
Bougainvillea - 2.1 0.300 0.57 0.36
Morus alba Anthocyanidins TiO2 caoted FTO Pt caoted FTO LiI/I2/pyridine Acetonitrile/propionitrile 6.1 0.49 0.52 - Patrocinio et al., 2009

U
Vaccinium myrtillus Anthocyanidins 1.0 0.59 0.61 -
Mirtus caulifora Anthocyanidins 3.9 0.45 0.56 -

AN
Hibiscus surattensis Anthocyanin TiO2 caoted FTO Pt caoted FTO TBAI/I2 Acetonitrile/ethylene 5.45 0.392 0.535 1.14 Fernando and Senadeera,
Sesbania grandiflora - carbonate 4.40 0.406 0.569 1.02 2008
Hibiscus rosasinensis - 4.04 0.400 0.633 1.02
Nerium oleander - 2.46 0.408 0.591 0.59
Ixora macrothyrsa - 1.31 0.403 0.568 0.30
Rhododendron arboretum - 1.15 0.402 0.637 0.29

M
Beet root Betailain TiO2 caoted FTO Pt caoted FTO KI/I2 Ethylene glycol/acetonitrile 2.95 0.357 0.3 0.402 Oprea et al., 2012
Citrus Sinensis Cyanine TiO2 caoted FTO Pt caoted FTO KI/I2 Ethylene glycol/acetonitrile 3.84 0.340 - 0.50 Calogero and Marco, 2008
Solanum melongena, L. Nasunin 3.4 0.350 - 0.40
Begonia - TiO2 caoted FTO Pt caoted FTO DMPImI/LiI/I2/ GT/TBP Acetonitrile 0.63 0.537 0.722 0.24 Zhou et al., 2011

D
Tangerine peel - 0.74 0.592 0.631 0.28
Rhododendron - 1.61 0.585 0.609 0.57
Fructus lycii - 0.53 0.689 0.466 0.17
Marigold
Perilla
Herba artmisiae scopariae
-
-
-
TE 0.51
1.36
1.03
0.542
0.522
0.484
0.831
0.696
0.682
0.23
0.50
0.34
China Ioropetal - 0.84 0.518 0.626 0.27
Yellow rose - 0.74 0.609 0.571 0.26
EP
Flower knotweed - 0.60 0.554 0.627 0.21
Bauhinia tree - 0.96 0.572 0.66 0.36
Petunia - 0.85 0.616 0.605 0.32
Lithospermum - 0.14 0.337 0.585 0.03
Violet - 1.02 0.498 0.645 0.33
C

Chinese rose - 0.90 0.483 0.619 0.27

Mangosteen pericarp - 2.69 0.686 0.633 1.17
Rose - 0.97 0.595 0.659 0.38
AC

Lily - 0.51 0.498 0.667 0.17

Coffee - 0.85 0.559 0.687 0.33
Broadleaf holly leaf - 1.19 0.607 0.654 0.47
Shisho leaves Shisonin TiO2 caoted FTO - - - 3.56 0.55 0.51 1.01 Kumara et al., 2006
Chlorophyll 3.52 0.432 0.39 0.59
Shisonin + chlorophyll 4.80 0.534 0.51 1.31
Butea monosperma Isobutrin TiO2 caoted FTO Pt caoted FTO DMPImI/LiI/I2/TBP Acetonitrile 4.67 0.58 0.641 1.8 Agarkar et al., 2011
Canna indica L. Cyanidin-3-scillabiose TiO2 caoted FTO Pt caoted FTO DMPImI/LiI/ I2/TBP Acetonitrile/valeronitrile 0.82 0.54 0.59 0.29 Luo et al., 2009

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Salvia splendens Salvianin 0.7 0.558 0.61 0.26

Cowberry Cyanidin-3-galactoside 0.4 0.556 0.54 0.13
Solanum nigrum Anthocyanin 1.01 0.54 0.51 0.31
Bixa orellana Bixin TiO2 caoted FTO Pt caoted FTO DMPImI/ LiI/I2/TBP methoxypropionitrile 1.1 0.57 0.59 0.37 Gomez-Ortiz et al., 2010

PT
Norbixin 0.38 0.53 0.64 0.13
Bixin ZnO caoted FTO 0.087 0.32 0.37 0.01
Norbixin 0.15 0.34 0.34 0.017
Black rice Anthocyanin TiO2 coated Pt coated KI/I2 Ethylene glycol/ 1.142 0.551 0.52 - Hao et al., 2006
Erythrina Carotenoid conductive glass conductive glass acetonitrile 0.776 0.484 0.55 -

RI
Rosa xanthina Anthocyanin 0.637 0.492 0.52 -
Kelp Chlorophyll 0.433 0.441 0.62 -
Capsicum Carotenoid 0.225 0.412 0.63 -
Myrtus cauliflora Anthcyanin TiO2 caoted FTO Pt caoted FTO LiI/I2 Acetonitrile/3-methyl-2- 9.0 0.59 0.54 - Polo and Iha, 2006

SC
Berberies buxifolia Anthocyanin oxazolidinone 6.2 0.47 0.36 -
Monascus purpereus Xanthomonascin_A TiO 2 caoted FTO Pt caoted FTO LiI/ BMII /I2/TBP Acetonitrile/valeronitrile 6.1 0.57 0.66 2.3 Ito et al., 2010
Gardinia fruit Crocin TiO2 caoted FTO Pt coated ITO KI/ I2 Ethylene carbonate/ 2.84 0.43 0.46 0.56 Yamazaki et al., 2007
Crocetin acetonitrile 0.45 0.58 0.60 0.16
Spinach extract Chlorophyll TiO2 caoted ITO Pt coated ITO - - 0.467 0.55 0.51 0.131 Chang et al., 2010
Ipomea leaf extract Chlorophyll 0.914 0.54 0.563 0.278

U
Pomegranate leaf extract Chlorophyll - - - - 2.05 0.56 0.52 0.597 Chang and Lo, 2010
mulberry extract Anthocyanin 1.89 0.555 0.53 0.548

AN
Chlorophyll + anthocyanin 2.8 0.53 0.49 0.722
Ixora coccinea - ZnO caoted ITO Pt coated ITO LiI/I2 Acetonitrile 2.65 0.21 0.29 0.33 Thambidurai et al., 2011
Mulberry - 2.90 0.23 0.30 0.41
Beetroot - 2.30 0.2 0.3 0.28
Delonix regia cyanidin 3-O-glucoside TiO2 caoted ITO Pt coated ITO LiI/I2 Acetonitrile 1.33 0.30 0.39 0.317 Senthil et al., 2011
TiO2LiI/ I2/PEO/TBP 0.84 0.30 0.48 0.245

M
Eugenia Jambolana Anthocyanidin LiI/I2 Acetonitrile 1.49 0.35 0.48 0.505
TiO2LiI/ I2/PEO/TBP 1.58 0.30 0.46 0.444
Bogainvillea brasiliensis - Au Nanoparticle Ag coated ITO Ce(NO3)3/Ce(NO3)3 Ethanol/water 5 0.249 0.364 0.454 Lai et al., 2008
loaded on
Garcinia suubelliptica - 6.48 0.322 0.331 0.691

D
TiO2 caoted FTO
Ficus Reusa Linn. - 7.85 0.520 0.289 1.18
Rhoeo spathacea - 10.9 0.496 0.273 1.49
Black berry Anthocyanin TiO2 caoted FTO Nanocarbon TE KI/I2 Anhydrous ethylene glycol 10.6 0.33 0.42 1.46 Zhu et al., 2008
coated FTO
Beet root Betanin TiO2 caoted FTO Pt caoted FTO LiI/I2 Acetonitrile 13.91 0.36 0.56 2.71 Sandquist and McHale,
3-methoxyproprionitrile 8.61 0.44 0.61 2.22 2011
Hibiscus flowers Anthocyanins TiO2 coated FTO Graphite coated - - 0.289 0.403 0.525 - Tobin et al., 2011
FTO
EP
Gardenia Yellow extract Geniposide, Crocin, Crocetin TiO2 coated FTO Pt coated FTO DMPImP/LiI/I2/TBP 3-methoxypropionitrile 0.96 0.54 0.62 0.32 Park et al., 2013
Gardenia Blue extract Crocin and Crocetin 0.53 0.44 0.69 0.16
Kerria japonica Xanthophyll TiO2 coated FTO Pt coated FTO Iodolyte AN 50 (Solaronix) - 0.5597 0.5839 0.6775 0.22 Hemalatha et al., 2012
Rosa chinensis Anthocyanin 0.8017 0.5433 0.664 0.29
Ivy gourd fruits -carotene TiO2 coated FTO Pt coated FTO LiI/I2/TBP 2-methoxypropionitrile 0.24 0.644 0.49 0.076 Shanmugam et al., 2013
C

Red frangipani flowers Cyanidins 0.94 0.495 0.65 0.301

- Not specified; FTO: Fluorine doped tin oxide; ITO: Indium doped tin oxide; DMPImI: 1,2-dimethyl-3-propylimidazolium iodine; TBP: 4-tert-butyl pyridine; TBAI: tetrabutylammonium iodide; GT: Guanidinium thiocyanate;
AC

BMII: butylmethylimidazoliumiodide; PEO: Polyethylene oxide

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Table 5: Approved naturally derived food Colorants in European Union (EU), Food and Drug Administration
(FDA) of USA and 7th Edition of Japans Specifications and Standards for Food Additives (JSSFA)

EU Name E-number USA Name U.S. CFR JSSFA Name Colours obtained
number
Curcumin E 100 Turmeric 73.600 Turmeric oleoresin and Yellow
Turmeric oleoresin 73.615 curcumin
Riboflavin E101 Riboflavin 73.450 - Yellow
Riboflavin-5-phosphate
Cochineal, carminic acid, E120 Cochineal extract, carmine 73.100 Cochineal extract and Pink to Red

PT
carmines carminic acid
Chlorophylls and E140 - Chlorophyll Green to olive
Chlorophyllins
Copper complexes of E141 Sodium Copper 73.125 - Bluish green

RI
Chlorophylls and chlorophyllin
Chlorophyllins
Caramels E150 (a-d) Caramel 73.85 Caramel (a-d) Brown
Vegetable carbon E153 - - Grey to black
Carotenes E160a Carrot oil 73.300 Carotene from carrot Golden yellow to

SC
-carotene 73.95 orange
Carotene from palm oil
Carotene from Dunaliella
Annatto, bixin, norbixin E160b Annatto extract 73.30 - Orange
Paprika extract, capsanthin, E160c Paprika, 73.340 Paprika color and Reddish orange

U
capsorubin Paprika oleoresin 73.345 oleoresin
Lycopene E160d Tomato lycopene extract, 73.585 - Orange red
tomato lycopene

-apo-8-carotenal (C30)
Ethyl ester of b-apo-8-
E160e
E160f
concentrate
-apo-8-carotenal
-
AN 73.90 -
-
Reddish orange
Yellow/Orange
carotenic acid (C30)
Lutein E161b - Marigold color Golden Yellow
M
Canthaxanthin E161g Canthaxanthin 73.75 - Orange pink
Beetroot red, betanin E162 Dehydrated beets (beet 73.40 Red beetroot Pink to red
powder)
Anthocyanins E163 Grape color extract 73.169 Grape skin color and Depending on pH gives
D

Grape skin extract 73.170 extract a wide range of colors

(enocianina) varying from Pink/red
- Blackcurrat color to mauve/blue
TE

- Toasted partially defatted 73.140 - Brown

cooked cottonseed flour
- Fruit Juice 73.250 - Varies
- Vegetable Juice 73.260 - Varies
- Saffron 73.500 - Orange Yellow
- - Monacus color Red
EP

- - Carthamus red Red

- - Carthamus yellow Yellow
- Not included
C
AC

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Fig. 1. Various applications of Natural dyes

PT
RI
U SC
AN
M
D
TE
C EP
AC

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Fig. 2. A schematic representation of enhanced resourse utilization and waste minimization in a natural textile dyeing

ENERGY

PT
W ATER CULTIVATION FORESTRY FOOD INDUSTRY
FERTILIZER
PESTICIDES

RI
e.g. Indigo, Madder,
W eld, Sawwort W ASTE = LEAVES
e.g. Teak, Eucalyptus

SC
W ASTE
e.g. Pressed berries, Pomegranate peel,
Onion peel, walnut husk,
CROP TIMBER INDUSTRY Olive mill waste water

U
W ASTE
W ASTE = BARK

AN
can be e.g. Ash tree bark, Alder,
utilized as
Animal feed
Soil conditioner
W OOD FOOD &

M
Adsorbent
BEVERAGES

ENERGY
AND EXTRACTION AND STANDERDIZATION

D
SOLVENT

TE W ASTE
EP
can be utilized as W aste Compost
DYESTUFF W aste Biofuel
Adsorbent
C

ENERGY
W ATER DYEING PROCESS W ASTE W ATER
DYEING AUXILARIES
AC

W ASTE W ATER CONTAINING

MINIMUM CHEMICAL LOAD
Reuse of spent
dye liquor for (Released to wastewater
lighter shades treatment plant)
DYED TEXTILES

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Fig. 3. Chemical structures of the main constituents of the natural dyes used in functional finishing of
textiles

Turmeric (Curcuma longa) Indian Rhubarb (Rheum emodi)

O O OH O OH
R1 R2

HO OH R1 R2
O
R1 =OCH3, R2 = OCH3 Curcumin

PT
R1=H, R2=CH3 Chrysophanol; R1=H, R2=CH2OH Aloe-emodin
R1 =OCH3, R2 =H Demethoxycurcumin R1=H, R2=COOH Rhein; R1=CH3, R2=OH Emodin;
R1 =R2 =H Bisdemethoxycurcumin R1=CH3, R2=OCH3 Physcion

RI
Weld (Reseda luteola) Eucalyptus (Eucalyptus globulus) Cutch (Acacia catechu)
R OH OH
OH OH
HO O
OH
HO O
HO O

SC
OH
OH
OH O
R Catechin
OH O
R= OH Luteolin R= OH Quercetin
R= H Apigenin R= OC12H22O9 Rutin

U
Onion (Alium cepa) Flos sophorae (Sophora japonica) Gallnut (Quercus infectoria) &

HO O
OH
OH

HO
AN
O
OH
OH
Pomegranate (Punica granatum)
COOH
O
O OH

HO OH
M
OH OC H O HO OH
OH O 12 22 9 HO O
OH O
Quercetin Rutin OH O
Gallic acid Ellagic acid
D

Indigo (Indigofera tinctoria) Gromwell (Lithospermum Berberry (Berberis aristata)

O H erythrorhizon) O
N OH O +
TE

N
O
CH 3
N OCH 3
H O
Indigo CH 3
OCH 3
O OH
OH
Berberine
EP

Shikonin

Cochineal (Dacylopius Coccus) Jackfruit (Artocarpus heterophyllus) Teak (Tectona grandis)

OH O HO OH R1 O OH
C

HO OH R3
HO O
O
HO COOH
AC

OH O CH 3 R2 O OH
OH
HO OH OH O R1=H, R2=H, R3=COOH Tectoquinone
OH Morol R1=OH, R2=OH, R3=CH3 Tectoleafquinone
Carminic acid

Madder (Rubia tinctorum & Rubia cordifolia) Henna (Lawsonia inermis)

O R1
R2 O
OH

R3
O R4
R1=OH, R2=OH, R3=H, R4=H Alizarin; R1=OH, R2=OH, R3=H, R4=OH Purpurin O
R1=OH, R2=COOH, R3=OH, R4=OH Pseudopurpurin; R1=OH, R2=CH3, R3=OH, R4=H Rubiadin Lawsone
R1=H, R2=OH, R3=COOH, R4=OH Manjistin R1=H, R2=OH, R3=H, R4=OH Xanthopurpurin

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Fig. 4. Schematic representation of Working of Dye sensitized solar cells

PT
RI
U SC
AN
M
D
TE
C EP
AC

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Many different kinds of applications of natural dyes are under active study.

Reports technological developments in natural textile dyeing and finishing.

Natural dye sensitized solar cells have been critically discussed.

Special attention has been given to recent developments in natural food colorants.

PT
Some newly discovered applications of natural dyes have also been highlighted.

RI
U SC
AN
M
D
TE
C EP
AC