a review on functional dyes on the basis of design

Saeed & al./ Appl. J. Envir. Eng. Sci. 5 N°1(2019) 99-112

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A review on Functional Dyes on the basis of Design, Development and

Hi-tech Applications

Muhammad Saeeda, MamoonaMunir

b, ZiabKhalid

a, SajidUllah

a, Maida Murtaza

a,

Gohar Farida, TayybaRehman

c, AleenaUmar

c, Mahmoud M. Elmaadawy*

d

(a) Department of Chemistry, Quaid-i-Azam University 45320-Islamabad, Pakistan.

(b) Department of Plant Sciences, Quaid-i-Azam University 45320-Islamabad, Pakistan.

(c) Department of Chemistry, University of Agriculture Faisalabad-38000, Pakistan.

(d)*Nuclear Materials Authority, P.O. Box 530-Cairo, Egypt.

Corresponding author. E-mail :[email protected]

Received 18Jan 2019, Revised 11 Feb 2019, Accepted 25Feb2019

Abstract

In this review, design and development of dyes (Functional, natural, aryl amine, inorganic, ethylene linked

planer rigid organic dyes) has been reported, beneficial for many applications, as dye sensitized solar cell

(DSSc), PDT, biomedical, photo chromic dyes, and optoelectronics. Photo chromic dyes have immense

applications in optoelectronic materials, ophthalmic lenses for eye wear technology, optical data storage

and in smart textiles due to their active response to light. Recent applications of functional dyes are in

medical, such as for photo dynamic therapy. Functional dyes also have application in pH sensors and

optical chemical sensors.

Keywords: Functional dyes, DSCs, PDT, optoelectronics, photosensitizer, ophthalmic lenses.

1. Introduction

As early as 1,500 B.C., Linen strips blue dyed were used to wrap Egyptian mummies with woad

or indigo (Isatis tinctoria) those wrappings although 3,500 years old, still retain their blue color. In Greco-

Roman times, the woad plant was used as a blue dye, while red color was achieved with the use of Kermes

insect. One precious animal dye with a glorious history which became available for home consumption in

Crete in 1,600 B.C. was Tyrian purple. This popular dye brought prosperity to Tyre from 1,500 B.C until

the Arabs’ conquest in 638 A. Commercial dyeing is to be one of the most ancient technical arts [1]. The

history of dyeing begins as early as 3,000 B.C., when process for dyeing fine fabrics, principally linen, in

a full range of hues had evolved. The dyeing industry no doubt originated in China before 3,000 B.C [2].

mailto:[email protected]


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Dye can be defined as aromatic organic material that has affection to the substrate and also need a

mordant to enhance the activity [3]. Dyes are however, the prime group can be used for recognition of

entity components of tissue section that can simply be used to our choice [4]. Dyes should be absolutely or

at least moderately soluble to substrate and are applied in the liquid form to abundant substrates such as

plastic, paper, textile and leather etc. [5]. Dyes are of many types such as (Acid, Basic, Mordant, Vat,

Reactive, Disperse, Azo, and Sulfur dyes), classified on the basis of stability and chemical properties.

Acidic dyes (anionic dyes) soluble in water are generally functional of fibers such as silk, nylon, wool etc.

Basic dyes (cationic dyes) are also soluble in water which are primarily applied on acrylic fibers. Direct

dyes have affinity to apply on wool, silk, nylon, leather, cotton, paper etc. Mordant dyes require a mordant

to develop the affinity of dye against H2O and light. Vat dyes (water insoluble) cannot directly apply on

fabric. Reactive dyes able to directly apply on fiber substrate because it made use of a chromophore

attached to substituent. Dyeing cellulose acetate are developed by disperse dyes (water insoluble). Sulfur

dyes (inexpensive) exploit to dye cotton with dark colors [6-8].

2. Properties of Dyes:

The composition of Dyes includes; (1 or 2) electrons donating group, conjugated bridge and anchoring

group as shown in Fig. 1. For grafting of dyes on the surface of semiconductor, Dyes have anchoring

group (phosphonate, carboxylate), to determine the near coupling of electronsamong the conduction band

and excited state [9]. Ultimate sensitizer for DSSc inject electrons to conduction band, absorb all light

below a threshold wavelength (920nm), resolutely attached to the surface of semiconductor oxide,

adequately redox potential, high heat stability and have suitable steric properties to overturn the charge on

TiO2 semiconductor surface [10].

Figure 1: Composition of Dye.

3. Functional dyes:

In 1981, Japanese scholar used the term functional dyes for the first time [11]. Hi-tech

applications based, (dye-affinity chromatography in biotechnology, PDT in biomedical, DSSc, Photo

Chromism, liquid crystals and imaging technologies are come out from functional dyes [12].

DSSc:

New profitable methods are required for the low cost and large volumes solar cells [13] reported

innovative type (DSSc solar cell) as shown in Fig.2. DSSc has consequences of photoelectric conversion

efficiency as a solar energy absorber. Gratzel type DSSc entail a Nano porous TiO2 film equipped on a


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translucent conductive glass (oxide). Nano porous TiO2 film is engrossed with a Pt-electrode (redox

couple) in an electrolyte. The electrons are shifted in the transmission band, disseminates through

absorbent Titanium dioxide within sensitizer. Reduction of oxidizable sensitizer molecules is occur in the

unique state within the pores through a redox couple of liquid electrolyte [14].

Figure 2: DSSc

DSSc in Solid State:

[15] reported the neutralization of compounds (dyes) can be done by penetrating electrons in hole

transport properties of P-type doping in TiO2 (Nano crystallized) that will solve the problems occur in

redox electrolyte. More than that efficiency of about 3.8% was attained by [15] utilizing hole conductor

Cu(I) in DSSc.

DSSc Mechanism:

For energy adaptation, the proficiency of DSSc depends on kinetics of electron transfer and relative E-

levels. The decay rate must be lower than rate of injection of electron, and rate of back reaction of DSSc

must be less than reduction rate for better efficiency of the DSSc at excited state [16]. Fig.3 illustrate the

mechanism of DSSc; adsorbed dye (D) is excited by a photon of light on the surface of semiconductor.The

excited dye (D*) has capacity to shift the electrons to surface of Titanium di-oxide[11].

Figure3:Gratzel type DSCs.


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4. Inorganic Dyes:

Photo sensitizers (conversion effectiveness of 11.2% and 10.4% for N3, N719 and Black Ru-dye

respectively) which are complexes of metal (Ru) with polypyridyl as shown in Fig.4 [17].

Figure 4: M-complexes of Ruthenium with polypyridyl (N719, N3 and Black dye).

Dye containing 2-electron donating groups:

Fig.5 shows the rate of electron injection to conduction band increased and (LUMO) is lowered by the

presence of 2-electron donating dyes as compared to 1-electron donating dyes [18-20].

(1) (2)

Figure 5: (1) and (2) Chemical structure of designed dyes contains two electron donating groups for

DSCs.

5. Natural Dyes:

Rather than artificial the dyes, natural dyes are low cost, easily available, biodegradable, and ecofriendly,

(e.g. cyanine as shown in Fig. 6) [21, 22]. Fruit peels as a natural dye utilized, [21] reported peel pigment

used as photo sensitizer with 0.47% efficiency and N,N-diethyl amino as donor moiety and [23] reported

the utilization of Musa aromatica peel with 0.21% cell efficiency. No more investigation is reported

regarding the fruit peels as a natural dye according the literature reviews of [24], [25], [26], and [27]. The


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present research and amendments extensively describe the improvement of cell performance by the

presence of donor group in natural dyes. In addition, further treatment for improvement of dyes such as

acid treatments [28], solvent effects [29], quantum dot coupling [30], dye combinations [31], dye

purifications [32], and combined TD-DFT-experiment [33].

Figure 6: Cyanine (Natural Dye).

6. Photo Chromic Dyes:

[34] reported the photo transformation of dye have diverse amalgamated spectra as shown in Fig.7.

Figure 7: Photo Chromism.

[35] reported that an external stimulus that respond the photon imperative endeavor for development of

photo chromic molecules that have applications (imaging devices, switches of molecules, smart window

sand photo morphogenesis). Fig.8 illustrate the mechanism of Spiro molecules (pyran and oxazine), when

they are irradiated in UV.

Figure 8: Mechanism of Pyran and Oxazine (Photo Chromism).


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[36] reported the preparation of highly transparent photo chromic compounds (gels), amalgamation of

flavylium in matrix of pluronic (Fig. 9). When we irradiate the 7-(N, N-diethylamino) 4-

hydroxyflavylium, as a chromophore, its color changes from yellow to red and it goes back in its original

form when put in dark.

Fig 9: Photo Chromism based on flavylium systems

Factors affecting the efficiency of DSSc:

The factors which causes to decrease the efficiency of DSSc; less stability of organic dyes, aggregation of

dye on semiconductor [37]. The nonplanar dyes (di-phenylaniline or di-arylaniline) show aggregation due

to 𝜋-𝜋 stacking. Efficiency of different DSSc materials is shown in Table. 1,2 [38, 39].

Table 1: Efficiency of some photo sensitizers:

Photo sensitizers η (%)

Ru- bipyridyl 11.2

Black Ru-dyes 10.4

Eggplant peel pigment 0.47

Tangerine peel 0.28

Musa aromaticalpeel 0.21

Rose 0.38

Acidified hesperidin 0.71

Neutralgallocatechin 0.26

Table 2: Efficiency of some Hole transfer materials:

Holetransfermaterials η (%)

Polyaniline 1.15

CuSCN 1.5

CuI 2.4

Spiro-OMeTAD 3.2

CuBr 3.8


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7. Hi-Tech applications of dyes:

7.1. Photo Chromic Materials:

On the basis of design and synthesis of photon responding molecules, there are diverse applications of

photo chromic materials including optoelectronic materials, ophthalmic lens, optical data storage, and

smart textiles. [40] reported the potential applications of organic photo chromic molecules in switches

devices and optical memory. [41] reported that, Indololinonapthooxazine (spiral) derivatives contributes

as multifunctional optoelectronic material due to their deep photo coloration, rapid thermal recreation and

low energy resistant.[42] reported the photo cleavage (C-O) under UV in above discussed molecule and

show absorption in visible region due to the formation of pi-conjugated molecule (PMC) as illustrated in

Fig. 10.

Figure 10: Formation of Pi-Conjugated PMC.

Photo chromic molecules have many expertise in eyes technology, e.g. benzopyran for the improvement

of ophthalmic lens and diphenyl napthopyrans appropriate for UV protecting goggle [43]. Current

development in I.T for enhance the ability of carriers and imperative process rate for the progress of light

sensitive materials in high capacity optical data storage when photo chromic materials are enthused by

different wavelength then they are interconvertable among 2-isomers and these isomeric forms in digital

mode shown by “0” and “1” [44]. Fig. 11 shows the photo mode recording of photo chromic hydro gel

based Napthaoxazine(Spiro) an optical data storage molecule [45].


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Figure 11: photo mode recording

Topical exploration is mounting for applications of Photo chromic molecules in textile industry (as shown

in Fig. 12) such as smart fashion and designing, enrich UV shielding, safekeeping motif and well-designed

effects by applying these dyes on fabrics[46].

Figure 12: Smart textile.

[47] reported the exhaustion process of Spiro molecule Oxazines on polyamide fiber but the percentage

value of these dyes was small due to less diffusion power and weak forces of attraction and adsorption

process of oxazine(spiro) on polyamide fiber analogous as non-ionic dyes which comprises at high

temperature and pressure. Figure 13 shows the confirmation of photo chromic response of dyed fiber. In

the effort to enhance the exhaustion % value, the dispersed oxazine (Spiro) surrounding with

trichlorotriazine was used for dyeing the polyamide fiber[48].


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Figure 13: Photo Chromic reaction of Dyes on polyamide fiber.

7.2. Biomedical Applications and Fluorescent Sensors:

These are the following applications of dyes in biomedical problems; PDT (a light activate treatment) used

in hospitals to abolish unhealthy tissues [49] and elimination of bacterial infections[50]. The PDT deed is

the combine use of photo sensitizers and light in which photosensitizer detect the unhealthy tissue and

switch thorough transfer of light [51].

7.3. Mechanism of Photo Sensitizer:

The dye molecules exhibit absorbance and transmittance of wavelength due to chromophore present in it

and shows specific colors in the visible region. The dyes absorb specific wavelength depend upon the

comparative position of electrons in ground state and excited state. The excited electrons are reversed to

the ground state by non radiative process (Fig 14). The absorbed light pass proficiently in neighborhood to

other molecules and utilized for photo chemical reactions is the major difference among the photo

sensitizer and other dyes. Thus the photo sensitizer (single state) is more stable, undergo reshuffle of

electrons to triplet excited state [52, 53].

Figure 14: Photosensitization Pathways.


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7.4. Use of Cyanine in Photo Dynamic Therapy:

Cyanine (a cationic sensitizer) also called photo therapeutic window of photo dynamic therapy absorbed

in Near-IR region having absorption value (𝜀>105). Certain cyanine’s (mero-cyanine and keto-caynine)

sued as a potential photo sensitizers in PDT [54] and as radiation sensitizers [55] in tumor medication.

Figure 15 Shows the MC540-structure have large scope in functionalization and appealing to chemists in

medicines [56].

Figure 15: chemical structure of merocyanine MC540.

[57] reported the study of cyanine photo sensitizers in the improvement of photo dynamic therapy agent

and cationic azo-cyanine having strong molar absorptivity (700nm) and negative solvatochromism

(Fig16).

(a)

(b)

Figure16: (a) Delocalized cationic azo dyes (b) Molar absorptivity.


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7.5. Fluorescent Sensor:

There is a need of fluorescence sensors having accessibility in diverse colors, as significance. A

fluorescence based technique having sensor function, non-destructive and highly sensitive provides

noteworthy benefits than the other techniques. Chemo sensors interact with cations, anions and neutral

molecule to change the electrical and optical properties[58].These sensors are multi purposed for

envisaging the molecules.Fluorescence Sensors comprises the three main edifice sites; linker (deliver

communique of electrons), reporter and receptor moiety exhibit high sensitivity and selectivity for trigger

the molecules. Communication of electrons are following three ways; overlapping of pi-system of

moieties through bridge, photo induced electrons are transferred through sigma-insertion, preparation of

moieties through interaction of supra molecules [59].

7.6. Cyanine-Marker in DNA:

Fluorescent molecules have ability to form complexes by physically and chemically combination with

labeled objects. The qualitative and quantitative information about labeled objects is transmitted by

measuring the fluorescent intensity. These dyes have much significance as lowdose, suitable uniformity,

highly detective and non-radiated [60]. As a consequence, Fluorescent techniques (highly sensitive) are

very significant than the other for determination of nucleic acid (non-fluorescence molecule) by

interaction with cyanine. In this way cyanine (dyes) have outstanding biological significance for DNA

detection as shown in Fig.17 [59, 61].

Figure 17: Binding of Cyanine with Nucleic acid.

7.7. Cyanine based pH-Sensor:

The Near-IR and visible spectra values of bio-molecules (auto fluorescence) is decreased in the range of

(700-800nm) due to the protonation and de-protonation, simultaneously variations in pH mode.

Fluorescence pH-Sensor is very useful in intra-cellular study. For significance, the need of cyanine based


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pH-Sensors is increasing [62, 63]. The outcomes indicate that the cyanine pH-Sensors has high sensitivity

to change the intra-cellular pH (6-8). It is recommended that the cyanine shows strong absorption, because

in involves resonance among the two N-atoms of two indole ring due the conjugated double bonds,

destruction of resonance occurs when proton is abstracted and successively non-fluorescence compound is

formed (Fig 18) [59].

Figure 18: Cyanine pH-Sensor.

Conclusion

Dye is a colored, ionizing and aromatic organic material that has affection to the substrate. On the basis of

stability and chemical properties, different dyes were discussed (Natural, Inorganic, Solid state, Photo

Chromic, DSSc). DSSc has efficiency to renovate solar energy into electrical than a conventional solar

cells. PDT used in health center's to obliterate the unhealthy tissues and bacterial virus. Fluorescent dyes

also used for determination of nucleic acid and are used as markers for DNA analyzing. Different dyes

also used as pH sensors.

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a review on functional dyes on the basis of design

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