application of azo-calix[4]pyrrole dyes in dyeing of...

CHAPTER 6

APPLICATION OF AZO-CALIX[4]PYRROLE

DYES IN DYEING OF FIBRES AND THEIR

ANTIMICROBIAL ACTIVITY

Dyeing & Antimicrobial Activity

Chapter 6 32

RESUME

In the present chapter dyeing properties of newly synthesized azo-

calix[4]pyrrole dyes on textile fibres like nylon, silk, wool, acrylic, cotton and paper

have been studied. Their fastness properties towards light, water, washing and acid-

alkali perspiration have also been studied. The position of colour in CIELAB

coordinates (L*, a*, b*, H* and C*) was assessed. The synthesized azocalix[4]pyrrole

dyes were screened for their antibacterial on S. aureus, E. coli and antifungal activity

on Rhizopus sp. and A. niger. These azo-calix[4]pyrrole dyes exhibit good

antimicrobial activity and bright shades on fabric with very good fastness properties.


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TABLE OF CONTENTS

1. Introduction 234

2. Experimental Section 238

2.1. Materials and instrumentation 238

2.2. Antimicrobial activities 239

2.2.1. General steps for evaluation of antimicrobial activities 239

2.2.2. General method used for the determination of 241

antimicrobial activity

2.3. Dyeing, color matching & fastness studies of azo-calix[4]pyrrole dyes 242

2.3.1. Scouring of fibres 242

2.3.2. Dyeing of fibres (nylon, silk, wool, acrylic hunk, 242

cotton and paper)

2.3.3. Colour measurements of dyed fibres 242

2.3.4. Fastness properties 244

3. Results and Discussion 245

3.1. Microbial screening of synthesized dyes 245

3.1.1. Antibacterial activity 245

3.1.2. Antifungal activity 246

3.2. Evaluation of colour parameters 246

3.3. Dyeing and fastness properties 247

Conclusion 269

References 270


Chapter 6 Page 234

1. INTRODUCTION

Calix[n]pyrrole [1] represents a new member of the calix[n]arene family

characterized by the presence of pyrrolic groups instead of phenolic moieties. This

makes calix[n]pyrrole very interesting molecule with many novel features when

compared with the chemistry of “classical” calixarenes [2]. A survey of the recent

literature reveals that calix[4]pyrroles have been mostly studied for the complexation

properties with anion, cation and neutral molecules [3]. There exists some research

wherein macrocycles such as crown ethers [4], calixresorcinarenes [5] and calixarenes

[6-9] have been used as components for the preparation of azo dyes, the research in

the area of azo-calix[4]pyrrole dyes has not evolved much.

Azo compounds are a significant class of organic colourants and consist of at

least one conjugated chromophore azo (-N=N-) group and two or more aromatic

rings. The colouring properties of organic dyes depend on both presence of the

chromophore groups and the crystallographic arrangement of molecules in the solid

state [10].

Dyes and pigments [11-13] are chemical components that are responsible for

much of the colour in the natural world and which are added to manufacture goods

such as textiles and foodstuffs to generate the desired colour. Dyes may be either

natural or synthetic in origin. Dyes are substances that can be used to impart colour to

other materials, such as textiles, foodstuffs and papers. Unlike pigments, dyes are

absorbed to a certain extent by the material to which they are applied. Colourants

obtained from animal or vegetable matter with little or no chemical processing are

known as natural dyes. The first synthetic dye “mauveine” was discovered by Milliam

Henry Perkin in 1856 and since then, many thousands of dyes have been prepared and

utilized. The dye is usually used as an aqueous solution and may require a mordant to


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improve the fastness of the dye on the fibre. Dyes can be classified according to their

chemical constitution or on the basis of their applications to fibres.

Acid dyes

An acid dye is sodium (less often–ammonium) salt of a sulfonic, carboxylic or

phenolic organic acid. Acid dyes are soluble in water and possesses affinity for

amphoteric fibres. When dyeing, ionic bonding with fibre, cationic sites accounts for

fixation of coloured anions in the dyed material. Acid is added to dyeing baths to

increase the number of protonated amino-groups in fibres. They can be applied on

fibres such as silk, wool, nylon and all of which contain basic groups. Few examples

are Alizarine, Nylomine, Coomassie etc.

Basic dyes

Gathering the requirements of various industries, superior quality Basic dyes

having bright brilliant shades and excellent values were prepared. Basic dyes are

water soluble cationic dyes; these dyes are used to be applied on acrylic fibres.

Moreover, they are also used to be applied on wool and silk. Apart from these, Basic

Dyes are also known for offering results on the Acrylic, Yarn, Paper, Jute, and

Leather. Few examples of basic dyes are Astrazon, Maxilon, sandocryl etc.

Direct (substantive) dyes

Direct dyes are a class of hot water dyes used on cellulose fibres, such as

cotton. Direct dyes provide the simplest means of dyeing cellulosic materials since a

single stage process, from neutral or slightly alkaline solution to which sodium

chloride or sulphate is added, normally applied as necessary to promote dye uptake.

Direct dyes are used on cotton, paper, leather, wool, silk, and nylon. They are also

used as pH indicators and as biological stains. Few examples of Direct dyes are

Chloramine, chlorazol etc.


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Mordant dyes

As the name suggests these dyes require a mordant. A mordant is a substance

used to set dyes on fabrics or tissue sections by forming a coordination complex with

the dye which then attaches to the fabric or tissue. It may be used for dyeing fabrics,

or for intensifying stains in cell or tissue preparations. The choice of mordant is very

important as different mordants can change the final colour significantly. A mordant

is often a polyvalent metal ion. The resulting coordination complex of dye and ion is

colloidal and can be either acidic or alkaline. Few examples of Mordant dyes are

Cochineal, Madder etc.

Vat dyes

Vat dyes are coloured, insoluble in water and incapable of dyeing fibres

directly. However, reduction in alkaline sodium hydrogen sulphite can convert them

to colourless soluble forms (leuco). In this leuco form, these dyes have an affinity for

the textile fibres. Subsequent oxidation by exposure to air or an oxidizing agent

reforms the original insoluble dye. Few examples of Vat dyes are Indigo, Tyrian

purple etc.

Reactive dyes

These dyes first appeared commercially in 1956 and were used to dye

cellulosic fibres. This dye contains a reactive group that, when applied to a fibre in a

weakly alkaline dye-bath, forms a chemical bond with the fibre. Reactive dyes can

also be used to dye wool and nylon, in the latter case they are applied under weakly

acidic conditions. Few examples of Reactive dyes are Cibacron, Drimarene etc.

Disperse dyes

They were originally developed for the dyeing of cellulose acetate. Disperse

dyes are substantially water insoluble. They are finely ground in the presence of a


Chapter 6 Page 237

dispersing agent, then sold as a paste or spray or dried as a powder. They can also be

used to dye nylon, triacetate, polyester and acrylic fibres. In some cases a dyeing

temperature of 130ºC is required and a pressurized dye-bath is used. The very fine

particle size gives a large surface area that aids dissolution to allow uptake by the

fibre. The dyeing rate can be significantly influenced by the choice of dispersing

agent used during grinding. Few examples of disperse dyes are Dispersol, Cibacet etc.

Azoic dyes

A dyeing technique, in which an insoluble azo dye is produced directly onto or

within the fibre, achieved by treating a fibre with a diazo component and a coupling

component. With suitable adjustment of dye-bath conditions, the two components

react to produce the required insoluble azo dye. This technique of dyeing is unique,

the final colour is controlled by the choice of the diazo and coupling components. One

of the example of Azoic dyes is Methyl orange.

Food dyes

One new class which describes the role of dyes, rather than their mode of use,

is the food dye. Because food dyes are classed as food additives, they are

manufactured to a higher standard than some industrial dyes. Food dyes can be direct,

mordant and vat dyes and their use is strictly controlled by legislation. Many are azoic

dyes, although anthraquinone and triphenylmethane compounds are used for colour

such as green and blue. Some naturally-occurring dyes are also used. Few examples

of food dyes are Orange B and Citrus Red 2 etc.

Sulphur dyes

The first sulphur dye was discovered in France in 1873, and further work done

by Raymond Videl enabled the manufacturing of 'Videl black". Its outstanding

fastness to light, washing and boiling far surpassed any cotton black known at that


Chapter 6 Page 238

time. Two disadvantages of sulphur dyes are that they produce dull shades and lack a

red colour. The main advantage lies in their cheapness, ease of application and good

wash fastness. In their normal state sulphur dyes are insoluble in water but are readily

soluble in the solution of sodium sulphide. In this form they have high affinity to all

the cellulose fibres.

Antimicrobial Activity

The investigation on antimicrobial activity of different types of compounds is

not only useful for the development of new drugs but it is also essential to ascertain

the toxic nature of the compound. Further, if a compound is to be used as a dye for a

fibre then it is always worthwhile to ascertain its biological properties in order to find

its biocompatibility. In the present work the biological activity in terms of their

growth inhibitory property on specific known bacterial and fungal cultures of the six

synthesized azo-calix[4]pyrrole dyes have been evaluated by the standard “disc

diffusion” method. Bacterial subcultures of Escherichia coli and Staphylococcus

aureus and fungal subculture of Aspergillus niger, Rhizopus sp. have been used as test

organisms and all the samples have been tested against these stains at different

concentrations. The dyeing performance of azo-calix[4]pyrrole dyes on fibres like

cotton, silk, nylon, wool, acrylic hunk and paper as well as their fastness properties

related to light, water, washing and perspiration have also been studied and discussed.

2. EXPERIMENTAL SECTION

2.1. Materials and instrumentation

All the reagents used were of AR grade, purchased from Sigma-Aldrich or

Merck and were used without further purification. All aqueous solutions were

prepared with deionised double distilled water, which was further purified by a


Chapter 6 Page 239

Millipore Milli-Q water purification system (Millipack 20, Pack name: Simpak 1,

Synergy). Colour coordinates (L*, a*, b*, H* and C*) were measured by Premier

colour scan 5100; computerized colour matching system with illuminates D65 with

10° observer. Six new tetra functionalized azo-calix[4]pyrrole dyes (Figure 1) were

synthesized and characterized as described in Chapter 2.

2.2. Antimicrobial activities

2.2.1. The evaluation of antimicrobial activity involved the following general steps:

Treatment of glass apparatus and its sterilization:

All the glass apparatus, including petri-dishes were cleaned with chromic acid

followed by washing with distilled water. These were then sterilized by heating at

120°C in an oven fully wrapped in inert foil for 6-8 hours.

Preparation of the media and its sterilization:

Nutrient agar and Czapek Dox agar slants were used as culture media for bacterial

cells and fungal spores respectively.

Composition of nutrient agar medium is:

Peptone = 5 gm, sodium chloride = 5 gm, beef extract = 1.5 gm, yeast extract = 1.5

gm, agar = 15 gm, distilled water = 1000 mL (pH = 7.40.2)

Czapek Dox Agar medium was composed of:

sodium nitrate = 2 gm, dipotassium hydrogen phosphate = 1 gm, magnesium sulphate

= 0.5 gm, potassium chloride = 0.5 gm, ferrous sulphate = 0.01 gm, sucrose = 30.0

gm, agar = 15 gm, distilled water = 1000 mL (pH = 7.30.2)

For preparation of the media, all ingredients except agar were dissolved in half of the

water with gentle warming wherever required. In the remaining half of the distilled

water, agar was dissolved by heating with constant stirring. The two solutions were


Chapter 6 Page 240

mixed and heated to make a homogenous solution. One liter solution of each media

was filtered through cotton and a clear solution was obtained. This was then sterilized,

properly plugged in a conical flask by autoclaving at 120°C for 30 minutes.

Pouring of the media into sterilized petri-dishes and its solidification:

15-20 mL of sterilized media was poured homogenously into sterilized petridishes

and used for the inoculation.

Inoculation of the media with the test organisms:

Bacterial cells (0.5 mL) or of fungal spore suspension (0.2-0.3 mL) was added to

the petridishes, prepared by the method as described above and spread with the help

of a sterile spreader. These petridishes were kept in laminar for 10 minutes for

inoculation.

Preparation of the solutions and control:

Standard 50 ppm solutions of compounds were prepared by appropriate dilution of

stock solution and used to study their antimicrobial activity.

Preparation of test plates:

Filter paper discs were soaked in the above solution of test compound and these

paper discs were placed on the petri dish and incubated at 37°C for 24 hours.

Measurement of the zone of inhibition:

Zone of inhibition was measured for each compound separately with respect to

control and also compared with standard drugs.


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NH

CH3

CH3 R1

OH OHN

NR1

R2

4

Azo-calix[4]pyrrole dyes

a : R1= H , R2= -CH3

b : R1= -NO2 ,R2= -NO2

c : R1= H ,R2= -OH

d : R1= H , R2= -Cl

e : R1= H , R2= -NO2

f : R1= -OH , R2= H

Figure 1. Six new tetra functionalized azo-calix[4]pyrrole dyes

2.2.2. General method used for the determination of antimicrobial activity:

A saturated solution of nutrient agar or Czapek Dox agar (75.0 gm) was

prepared in double distilled water and it was autoclaved for 15 minutes, and then

poured into petri dishes in the laminar. After its solidification loan of bacteria (i.e

Escherichia coli and Staphylococcus aureus) or fungi (i.e. Asperillus niger and

Rhizopus sp.) against which antimicrobial activity is to be investigated was applied.

Paper discs were soaked in 50 ppm solution of all the azo-calix[4]pyrrole dyes for 10

minutes These paper discs were then placed in petri-dishes and were kept in incubator

at 37°C for 24 hours, they were then removed and the zone of inhibition was

measured in mm.


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2.3. Dyeing, colour matching & fastness studies of azo-calix[4]pyrrole dyes

2.3.1. Scouring of fibres

In order to remove the wax, oil, resin and colouring matter from the fibre, they

were scoured by standard method with a solution of 2.0 gm sodium hydroxide and 2.0

gm common detergent, were mixed in 200 mL water and then 3.5 gm fibre hunk was

added to this. The mixture was boiled for 3 hours and then allowed to cool at room

temperature; the hunk was washed thoroughly with water to completely remove the

adhered caustic soda and detergent.

2.3.2. Dyeing of fibres (nylon, silk, wool, acrylic, cotton and paper)

Stock solution was prepared by dissolving 1.0 gm of azo-calix[4]pyrrole dyes

in 5 mL, 0.1% NaOH solution and then the volume was made up to 500 mL with hot

water. 20 mL of solution was pipette out, added to 0.5 mL, 20% acetic acid and 5.0

mL, 30% sodium sulphate solution; volume was made upto 100 mL. The scoured

fibre hunk (2 gm) was then added to this solution in dyeing bath and its temperature

was raised gradually to (~100°C) in 45 minutes and was maintained for 30 minutes

with periodic check on exhaustion of dye. On the completion of dyeing, the dyed

hunk samples were removed, rinsed in cold water to remove any loosely adsorbed dye

and dried in air.

2.3.3. Colour measurements of dyed fibres

The colour matching of the dyed fabrics with standard has been studied by

computerized Premier colour scan 5100. The colour parameters were evaluated by

means of the CIE [Commission Internationale de l’Eclairage (CIE)] lab (D65/10°)

system [14].The following colour parameters for the dyed samples were obtained by


Chapter 6 Page 243

the digital CIE lab system [15]: L*- lightness, a*- redness if positive coordinate or

greenness if negative coordinate, b*- yellowness if positive coordinate or blueness if

negative coordinate, ∆H-difference in hue, C*- chromaticity.

The percentage dye bath exhaustion E was calculated by Eq. (1).

E =

o

do

AAA

100 (1)

where A0 and Ad are the respective absorbance of azo-calix[4]pyrrole dyes, initially in

dye bath and residual dye in the dye bath respectively.

For the dyed fabric samples, the light diffuse reflectance measurements were

performed with a computerized Premier colour scan 5100, and the colour yield values

were calculated according to the Kubelka-Munk function (K/S) [15] by Eq. (2).

SK =

RR

21 2 (2)

Where: K- absorbance; S- scattering; R- reflectance.

The values of colour difference (∆E) [15] for the dyed samples after relative

treatments were calculated by Eq. (3).

∆E = 222 )()()( baL (3)

Where: ΔL*=L*trl-Lin, ; Δa=atrl-ain, ; Δb=btrl-bin

L*trl, atrl, and btrl are parameters of trials, i.e. after blank dyeing (treatment of undyed

fabric under dyeing conditions, but without using dye) or after washing the dyed

fabric samples.


Chapter 6 Page 244

Lin, ain, and bin are parameters of initial species before the relevant treatments.

The ΔE deviation of all treated samples was no higher than 0.2.

2.3.4. Fastness properties

Coloured fibres withstand conditions like exposure to light, washing, perspiration

etc. during their subsequent use. Because these conditions usually result in alteration

in depth, or in hue, or in brightness of the fibres. The details of various fastness tests

are mentioned below and the results are given in Table 9.

Fastness to water [ISO 105/E 1978]

Pair of dyed and undyed specimen was immersed in water for 30 minutes thereafter

water was drained and the hunks were dried separately and the change in colour of the

dyed hunks and the staining of the undyed hunks were assessed by means of the

standard grey scale, where a rating of 5 is considered excellent and 1 as poor.

Fastness to washing [IS 764 (ISO 105-C03-test-3)]

Pair of dyed and undyed specimen was immersed in 0.5% common detergent solution

and was agitated for 30 minutes at 40-45°C. The specimens were removed, rinsed

three times with water and then dried by pressing with iron. Change in colour was

assessed using the standard gray scale; where a rating of 5 is considered excellent and

1 as poor.

Fastness to perspiration [ISO-105-E04-1994 (E)]

Both acidic and alkaline solutions were used in this test. The acidic condition was

simulated by a solution containing 1% sodium chloride, 0.1% disodium hydrogen

phosphate and 0.1% lactic acid. The alkaline condition was simulated by a solution

containing 1% sodium chloride, 0.1% disodium hydrogen phosphate, and 0.4%

ammonium carbonate. The tests were carried out in dry atmosphere at 38-40°C in


Chapter 6 Page 245

glass test tube. Pair of dyed and undyed specimen were rolled together in such a way

that they just fit into the tubes. The test specimen was thoroughly wetted with the acid

solution or alkaline solution with one-third of the roll remaining outside the tube. The

change in colour of the dyed and staining of the undyed specimen were assessed.

Fastness to light [ISO-105 (BS 1006) B01 (UK-TN)]

The dyed specimen was exposed to xenon test for 10 hours in which half of the

dyed material was kept unexposed. The specimen was then evaluated for its colour

loss. The reference standard chosen for light fastness is a series of eight blue dyes on

wool where a rating of 8 is considered excellent and 1 as poor.

3. RESULTS AND DISCUSSION

3.1. Microbial screening of synthesized dyes

3.1.1. Antibacterial activity

The antibacterial activity of the compounds against E.coli and S.aureus were

carried out using nutrient agar or Czapek Dox agar (75.0 gm. The activity, reported in

(Figure 2, Table 1), was carried out using paper disc method. The solutions of all

compounds were prepared at two different concentrations and chloramphenicol was

used as a reference for antibacterial studies. The plates were then incubated for 18

hours at room temperature. Among the various compounds, meso-tetra(methyl) meso-

tetra{(3, 5-dihydroxy phenyl)- 4-(2,4-dinitrophenyl diazene)} calixpyrrole (2b), meso-

tetra(methyl) meso-tetra{(3, 5-dihydroxy phenyl)- 4-nitrophenyl diazene)}

calixpyrrole (2e), meso-tetra(methyl) meso-tetra{(3, 5-dihydroxy phenyl)- 4-(2-

diazenyl phenol}) calixpyrrole (2f), has been found to be most effective against these

microbes showing maximum clarity of zones, its antibacterial activity was found

maximum against S.aureus.


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3.1.2. Antifungal activity

The antifungal activity of these compounds was checked by the agar plate

technique for the Rhizopus sp. and A. niger fungi. Fluconazole was used as a

reference for antifungal studies. The compounds were directly mixed to the medium

in different concentrations. The fungus was placed on the medium and incubated at

28°C for 3-5 days. The growth of fungus was measured by recording the diameter of

fungal colony.

The following relation calculated the fungal growth inhibition:

Fungal growth inhibition (%) = A – B/A x 100

where A is the diameter of the fungal colony in the control plate and B is the diameter

of the fungal colony in the test plate. Among all compounds meso-tetra(methyl) meso-

tetra{(3, 5-dihydroxy phenyl)- 4-(4-diazenylphenol)} calixpyrrole (2c), had shown

maximum antifungal activity. Results are represented in (Figure 3, Table 2).

3.2. Evaluation of colour parameters

Colour is associated with several aspects that create feelings and sensations or

stimulus in the observer’s mind. If the primaries chosen are red, green, and blue, a

very large numbers of colours can be matched. Based on this theory, in 1931 the CIE

[Commission Internationale de l’Eclairage (CIE)] [16] developed a system for

specifying colour. In 1976 the CIE specified a new colour space known as CIE 1976

(L*, a*, b*) colour space or CIELAB. CIELAB allows the specification of colour

stimuli in terms of a three-dimensional space. The L* axis is known as the lightness

and extends from 0 (black) to 100 (white). The other two coordinates a* and b*

represent redness-greenness and yellowness-blueness respectively. If ∆L* is


Chapter 6 Page 247

positive/negative the sample is lighter/darker than the standard. If ∆C* (chroma) is

positive/negative the sample is stronger/weaker than the standard. ∆H indicates

difference in hue.

In the present work, the application of azo-calix[4]pyrrole dyes for dyeing on

nylon, silk, wool, acrylic, cotton fibres and paper is described. Their L*, a*, b* values

as well as the colour difference values such as L*, a*, b*, C*, and H have

been reported. ∆L value are negative for dyes 2b on nylon fibre, dyes 2a-2e on silk,

dyes 2c, 2d on wool fibre, dyes 2c, 2f on acrylic fibre, dyes 2a, 2d, 2f on paper and

dyes 2d, 2f on cotton fibres, which suggest that these samples are darker than the

standard taken. The chroma-values (∆C) were negative for dye 2a, 2b, 2e, 2f on nylon

fibre, dyes 2b, 2c, 2d, 2e on silk fibre, 2a on wool fibre, dyes 2a, 2b, 2c, 2f on acrylic

hunk, and dyes 2d, 2f on paper and dyes 2d, 2f on cotton fibres, indicating their duller

effect. The results on colour coordinates of the samples are given in Table 3-8.

3.3. Dyeing and fastness properties

Seeing the physical properties and structures of azo-calix[4]pyrrole dyes, it

was observed that they may be categorized as direct dyes for the dyeing of nylon,

silk, wool, acrylic, cotton fibres and paper. Various studies like effects of dyestuff

concentrations, salt concentrations, pH on shade (reflectance) have been studied.

The actions of varying percentage (%) of dye concentrations showed that with

the increase in dye concentration from 0.2 % to 0.4 %, there was an increase in

reflectance on the fibres (Figure 4). After this concentration, the change in the values

of reflectance is minor which suggests the greater availability of dyestuff at low

concentration in solution and its penetration into the fibre materials. The effect of

variation in the concentration of salt from 0.5 to 8.0 % was assessed on dyed fibres.


Chapter 6 Page 248

The results showed that 2.0 to 5.0 % of aqueous salt did not have much effect on the

reflectance of the fibres (Figure 5). The fibres were dyed at various pH between 2.0-

10.0 and its effect was studied by the reflectance measurements, it was observed that

the dyeing capacity was maximum between pH 6.0 and 8.0 (Figure 6).

Because of very brilliant colour of dyed nylon, the fastness properties (fastness

to water, washing, acid-alkali perspiration and light) were carried out only on nylon

fibres. The results are summarized in Table 9.

In all cases the change in colour of the dyed specimen and the staining of the

undyed specimen was assessed using the standard grey scale. The results show that

fastness to water, washing, acid and alkali perspiration were at the level 4 to 5,

indicating very slight alteration in the shade or loss in depth of the dye. Light fastness

is the degree to which a dye resists fading due to light exposure. Different dyes have

different degrees of resistance to fading by light. All dyes have some susceptibility to

light damage, simply because their strong colours indicate that they absorb the

wavelength that they don’t reflect back. Light fastness is judged on a scale of 1 to 8,

where 8 is considered as excellent resistance to light. The light fastness of dyeing on

the nylon was of level 4-5, which indicates slight colour loss of dyed fibre. Different

shades of various dyed fibres have been demonstrated in Figure 7-11.


Chapter 6 Page 249

Table 1. Antibacterial activity of synthesized dyes

No Compound S.Aureus E.Coli i DMSO 0 1 ii Chloramphenicol 10 13

2a meso-tetra(methyl) meso-tetra{(3, 5-

dihydroxy phenyl)- 4-(4-methyl phenyl diazene)} calixpyrrole

6 3

2b meso-tetra(methyl) meso-tetra{(3, 5-

dihydroxy phenyl)- 4-(2,4-dinitrophenyl diazene)} calixpyrrole

8 5

2c meso-tetra(methyl) meso-tetra{(3, 5-

dihydroxy phenyl)- 4-(4-diazenylphenol)} calixpyrrole

6 5

2d meso-tetra(methyl) meso-tetra{(3, 5-dihydroxy phenyl)- 4-chlorophenyl

diazene)} calixpyrrole 4 6

2e meso-tetra(methyl) meso-tetra{(3, 5-

dihydroxy phenyl)- 4-nitrophenyl diazene)} calixpyrrole

8 5

2f meso-tetra(methyl) meso-tetra{(3, 5-

dihydroxy phenyl)- 4-(2-diazenyl phenol}) calixpyrrole

8 7

Chloramphenicol has been taken as reference.


Chapter 6 Page 250

Table 2. Antifungal activity of synthesized azo-calix[4]pyrrole dyes

No Compound Rhizopus sp. A. niger

i DMSO 0 1 ii Flucanozole 18 13

2a

meso-tetra(methyl) meso-tetra{(3, 5-dihydroxy phenyl)- 4-(4-methyl phenyl diazene)} calixpyrrole

7 8

2b

meso-tetra(methyl) meso-tetra{(3, 5-dihydroxy phenyl)- 4-(2,4-

dinitrophenyl diazene)} calixpyrrole 10 9

2c

meso-tetra(methyl) meso-tetra{(3, 5-dihydroxy phenyl)- 4-(4-

diazenylphenol)} calixpyrrole 11 8

2d

meso-tetra(methyl) meso-tetra{(3, 5-dihydroxy phenyl)- 4-chlorophenyl


2e

meso-tetra(methyl) meso-tetra{(3, 5-dihydroxy phenyl)- 4-nitrophenyl


2f

meso-tetra(methyl) meso-tetra{(3, 5-dihydroxy phenyl)- 4-(2-diazenyl

phenol}) calixpyrrole 10 9

Flucanozole has been taken as reference.


Chapter 6 Page 251

Table 3. Colour coordinate values for azo-calix[4]pyrrole dyes on nylon fibre.


L* Std. (Found)

a* Std. (Found)

b* Std. (Found)

C* Std. (Found)

H* Std. (Found)

L* a* b* C* H* E K/S Strength

(%)

2a 49.810

(49.715) 18.312

(18.389) 35.827

(35.846) 39.790

(39.832) 64.184

(64.090) 0.095 -0.077 -0.019 -0.042 0.065 0.121 9.48 100.35

2b 71.860

(71.883) 7.278

(7.401) 27.413

(27.437) 28.325

(28.418) 75.079

(74.874) -0.023 -0.122 -0.024 -0.092 0.102 0.139 13.54 101.46

2c 48.424

(48.394) 24.489

(24.532) 44.389

(44.205) 50.697

(50.556) 61.089

(60.947) 0.030 -0.043 0.184 0.141 0.126 0.191 12.83 100.15

2d 64.409

(64.481) 21.960

(21.884) 81.244

(81.346) 84.160

(84.238) 74.844

(74.912) 0.072 -0.076 0.102 0.079 0.100 0.146 31.96 101.8

2e 52.356

(52.203) 23.750

(23.851) 50.485

(50.638) 55.792

(55.974) 64.780

(64.753) 0.150 -0.101 -0.153 -0.182 0.027 0.253 13.14 101.91

2f 66.571

(66.548) 15.711

(15.708) 45.356

(45.374) 48.000

(48.016) 70.866

(70.876)

0.023 0.003 -0.018 -0.016 -0.009 0.029 31.89 100.31


Chapter 6 Page 252

Table 4. Colour coordinate values for azo-calix[4]pyrrole dyes on silk fibre.

Azo- calix[4]pyrrole

dyes

L* Std. (Found)

a* Std. (Found)

b* Std. (Found)

C* Std. (Found)

H* Std. (Found)


(%)

2a 57.059

(57.110) 16.550

(16.400) 41.598

(41.517) 43.810

(43.740) 67.492

(67.467) -0.051 0.150 0.081 0.070 0.025 0.107 8.75 100.18

2b 74.150

(74.201) 5.876

(5.993) 16.514

(16.621) 15.550

(15.653) 84.730

(84.720) -0.051 -0.117 -0.107 -0.103 0.010 0.170 4.28 99.87

2c 64.392

(64.538) 6.065

(6.048) 28.240

(28.274) 28.084

(28.115) 75.115

(75.135) -0.146 0.017 -0.034 -0.031 -0.020 0.150 20.73 98.50

2d 59.228

(59.172) 18.859

(18.929) 62.436

(62.376) 64.265

(64.229) 72.906

(72.830) -0.056 0.070 -0.060 -0.037 -0.085 0.108 17.58 98.23

2e 64.350

(64.365) 9.285

(9.297) 25.803

(25.836) 26.687

(26.748) 74.128

(74.161) -0.015 -0.012 -0.033 -0.061 -0.015 0.068 6.03 99.95

2f 59.654

(59.639) 15.720

(15.620) 38.533

(38.491) 39.691

(39.616) 67.251

(67.351) 0.015 0.100 0.042 0.075 -0.071 0.103 5.17 101.73


Chapter 6 Page 253

Table 5. Colour coordinate values for azo-calix[4]pyrrole dyes on wool fibre.

Azo-

calix[4]pyrrole dyes

L* Std. (Found)

a* Std. (Found)

b* Std. (Found)

C* Std. (Found)

H* Std. (Found)


(%)

2a 60.599

(60.549) 17.415

(17.477) 46.390

(46.455) 49.551

(49.634) 69.396

(69.355) 0.050 -0.062 -0.065 -0.083 0.035 0.103 2.35 100.95

2b 77.559

(77.521) 9.158

(9.085) 39.813

(39.699) 40.853 (40.725

77.015 (77.079)

0.038 0.073 0.114 0.127 -0.046 0.141 11.89 99.48

2c 55.644

(55.689) 15.817

(15.623) 37.533

(37.491) 40.691

(40.616) 67.251

(67.351) -0.045 0.194 0.042 0.075 -0.071 0.103 5.17 100.33

2d 56.884

(56.791) 29.849

(29.946) 68.361

(68.413) 74.593

(74.680) 66.385

(66.333) -0.093 0.097 0.052 0.087 -0.068 0.144 26.84 99.019

2e 62.445

(62.422) 7.097

(7.066) 24.543

(24.497) 25.549

(25.496) 73.842

(73.880) 0.023 0.031 0.046 0.053 -0.017 0.060 5.10 99.97

2f 59.644

(59.639) 15.717

(15.623) 37.533

(37.491) 40.691

(40.616) 67.251

(67.351) 0.005 0.094 0.042 0.075 -0.071 0.103 5.17 100.33


Chapter 6 Page 254

Table 6. Colour coordinate values for azo-calix[4]pyrrole dyes on acrylic fibre.


dyes

L* Std. (Found)

a* Std. (Found)

b* Std. (Found)

C* Std. (Found)

H* Std. (Found)


(%)

2a 81.340

(81.278) 5.885

(5.875) 33.015

(32.985) 33.530

(33.504) 79.859

(79.870) 0.062 0.010 -0.030 -0.027 0.006 0.065 6.99 98.45

2b 88.063

(88.059) -1.170

(-1.133) 9.084

(9.094) 9.159

(9.164) 97.372

(97.135) 0.004 -0.037 -0.010 -0.005 0.038 0.039 1.36 103.95

2c 59.078

(58.913) 13.518

(13.479) 32.972

(32.793) 35.636

(35.455) 67.680

(67.629) -0.165 -0.039 -0.179 -0.180 -0.032 0.247 11.62 99.15

2d 51.567

(51.692) 38.571

(38.556) 64.468

(64.785) 75.126

(75.390) 59.084

(59.218) 0.125 -0.015 0.317 0.265 0.175 0.341 38.00 100.72

2e 59.614

(59.635) 10.330

(10.271) 29.580

(29.638) 31.332

(31.367) 70.721

(70.858) 0.021 -0.059 0.058 0.035 0.075 0.085 18.44 100.53

2f 59.078

(58.913) 13.518

(13.479) 32.972

(32.793) 35.636

(35.455) 67.680

(67.629) -0.165 -0.039 -0.179 -0.180 -0.032 0.247 11.62 98.95


Chapter 6 5

Table 7. Colour coordinate values for azo-calix[4]pyrrole dyes on paper.


L* Std. (Found)

a* Std. (Found)

b* Std. (Found)

C* Std. (Found)

H* Std. (Found)


(%)

2a 81.624

(81.601)

6.749

(6.701)

35.041

(35.056)

35.685

(35.691)

79.066

(79.147) -0.023 -0.048 0.015 0.006 0.050 0.055 11.85 100.78

2b 44.759

(44.728)

32.230

(32.257)

44.626

(44.551)

55.048

(55.003)

54.140

(54.072) 0.031 -0.027 0.075 0.045 0.066 0.089 21.37 100.34

2c 64.146

(64.127)

7.942

(7.923)

26.364

(26.339)

27.534

(27.505)

73.206

(73.229) 0.019 0.019 0.025 0.029 -0.011 0.037 6.69 101.32

2d 79.109

(79.079)

5.833

(5.647)

69.614

(69.554)

69.858

(69.783)

85.176

(85.324) -0.030 -0.186 -0.060 -0.075 0.180 0.198 5.144 98.63

2e 78.559

(78.521)

9.158

(9.085)

39.813

(39.699)

40.853

(40.725

77.015

(77.079) 0.038 0.073 0.114 0.127 -0.046 0.141 11.89 98.48

2f 81.337

(81.278)

5.885

(5.874)

33.010

(32.985)

33.530

(33.504)

79.859

(79.870) -0.059 -0.011 -0.025 -0.027 0.006 0.065 6.99 99.64


Chapter 6 Page 256

Table 8. Colour coordinate values for azocalix[4]pyrrole dyes on cotton.


dyes

L* Std. (Found)

a* Std. (Found)

b* Std. (Found)

C* Std. (Found)

H* Std. (Found)


(%)

2a 59.614

(59.635) 10.330

(10.271) 29.580

(29.638) 31.332

(31.367) 70.721

(70.858) 0.021 -0.059 0.058 0.035 0.075 0.085 18.44 100.27

2b 77.559

(77.521) 9.158

(9.085) 39.813

(39.699) 40.853 (40.725

77.015 (77.079)

0.038 0.073 0.114 0.127 -0.046 0.141 11.89 99.48

2c 57.593

(57.580) 31.317 (31.307)

6.570 (6.533)

31.999 (31.981)

11.843 (11.782)

0.013 0.010 0.037 0.017 0.034 0.040 15.32 99.763

2d 70.163

(70.112) 13.499

(13.325) 41.824

(41.715) 43.948

(43.792) 72.083

(72.256) -0.051 -0.174 -0.109 -0.157 0.132 0.212 13.4 100.99

2e 51.072

(51.033) 28.318 (27.851)

4.573 (4.588)

28.685 (28.226)

9.170 (9.351)

0.039 0.467 -0.015 0.458 -0.090 0.469 11.54 101.108

2f 56.578

(56.590) 20.916 (21.277)

19.385 (19.325)

28.518 (28.743)

42.807 (42.231)

-0.012 -0.361 0.060 -0.225 0.288 0.366 12.64 99.256


Chapter 6 Page 257

Table 9. Various fastness properties of azo-calix[4]pyrrole dyes on Nylon fibre and their colour shades.

Azo-calix[4]pyrrole

Dyes

Shades on nylon fibre

Fastness to

Watera Washing staining

Washing colourb

Acid perspirationc

Alkali perspirationc Lightd

2a

Mustard Yellow 4-5 4 4-5 4.25 4 4.25

2b Light Pink 4-5 4-5 4 4-5 4 4

2c Dark Pink 4 4 4-5 4.25 4 4

2d Dark yellow 4-5 4 4-5 4 4.25 4.5

2e

Mustard Yellow 5 4-5 4-5 4 4-5 5

2f Dark Pink 4 4.25 4-5 4 4.5 4.5

a Water fastness test done as per ISO 105/E 1978. b Colour fastness of textile materials to washing staining and washing colour change of adjacent fabric as per IS 764 (ISO 105-C03-Test-3). c Fastness to acid/alkali perspiration test done as per ISO 105-E04-1994 (E). d Colour fastness to light done as per ISO 105 (BS1006) B01 (UK-TN).


Chapter 6 Page 258

Figure 2. Graphical Representation of antimicrobial activity

of azo-calix[4]pyrrole dyes.


Chapter 6 Page 259

Figure 3. Graphical Representation of antifungal activity

of azo-calix[4]pyrrole dyes


Chapter 6 Page 260

Figure 4. Effect of concentration of dyes on fibres.


Chapter 6 Page 261

Figure 5. Effect of salt concentration of the dyed fibres.


Chapter 6 Page 262

Figure 6. Effect of pH on the dyed fibres.


Chapter 6 Page 263

Figure 7. Photographic representation of synthesized azo-calix[4]pyrrole dyes applied on Nylon Fibre.


Chapter 6 Page 264

Figure 8. Photographic representation of synthesized azo-calix[4]pyrrole dyes

applied on Silk Fibre.


Chapter 6 Page 265


applied on Wool Fibre.


Chapter 6 Page 266


applied on Acrylic hunk fibre.


Chapter 6 Page 267


applied on Paper Fibre.


Chapter 6 Page 268


applied on Cotton Fibre.


Chapter 6 Page 269

CONCLUSION

A series of new azo-calix[4]pyrrole supramolecular dyes have been examined

and showed reasonably good antimicrobial activity against selected microbes namely,

E. coli, S. aureus and A. niger, Rhizopus sp. These azo-calix[4]pyrrole can be

considered as a good candidate for dyeing cotton, silk and wool fibres because of easy

dyeing process, no after-treatment process required. Further, the dyed fabric showed

good light fastness and good to excellent fastness to water, washing, staining and

acid-alkali perspiration. This indicates that the azocalix[4]pyrrole dyes have good

compatibility with the fabric.


Chapter 6 Page 270

REFERNCES

1. V. K. Jain and H. C. Mandalia, Heterocycles, (2007), 71, 1261.

2. (a) J. Vicens, and V. Bohmer, (Eds.), ‘Calixarenes, a Versatile Class of

Macrocyclic Compounds’, Kluwer Academic Publisher, Dordrecht, (1991).

(b) C. D. Gutsche, Calixarene revisited, The Royal Society of Chemistry;

Cambridge, (1998). (c) Z Asfari, V Bohmer, J Harrowfield and J Vicens,

Calixarenes (Kluwer Academic Publishers: Netherlands, 2001. (d) J. L.

Atwood, and J. W. Steed, ‘Encyclopedia of Supramolecular Chemistry’,

Marcel Dekker, Inc. New York, (2004).

3. (a). B. Garg, T. Bisht and S. M. S. Chauhan, New J. Chem.,(2010), 34, 1251.

(b) M. Chas, G. Gil-Ramı´rez, E. C. Escudero-Ada´n, J. Benet-Buchholz and

P. Ballester , Org. Lett., (2010), 12,1740. (c) V. K. Jain, H. C Mandalia,

Macroheterocycles, (2009), 2(1), 23.

4. (a) U. Harikrishnan and S. K. Menon, Dyes and Pigments, (2008), 77(2), 462.

(b) O. Farhana, D. B. Isabelle and L. Roger, Supramol. Chem., (2005), 17(3),

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5. (a) V. K. Jain and P. H. Kanaiya, J. Incl. Phenom. Macrocycl. Chem., (2008),

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(2008), 5(5), 1037. (c) Y. Ge, L. Liu, J. J. Meng and C. G. Yan, Chinese

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Publications

Azocalix[4]pyrrole Amberlite XAD-2: New polymeric chelating resins for the extraction, preconcentration and sequential separation of Cu(II), Zn(II) and Cd(II) in natural water samples Vinod K. Jain*, Hiren C. Mandalia, Hrishikesh S. Gupte, Disha J. Vyas Talanta 79 (2009) 1331–1340

Supervanadophile: Complexation, Preconcentration and Transport Studies of Vanadium by Octa Functionalized Calix[4]resorcinarene-Hydroxamic Acid V.K. Jain,*, S.G. Pillai and H.S. Gupte J. Iran. Chem. Soc., Vol. 5, No. 4, December 2008 Azo resorcin[4]calixpyrrole grafted Amberlite XAD-2 polymer: An efficient solid phase extractant for separation and preconcentration of La(III) and Ce(III) from natural geological samples Hrishikesh S. Gupte , Disha J Vyas, Bharat A Makwana, Keyur D. Bhatt And Vinod K. Jain* (Communicated)

Amberlite XAD-2 impregnated Azo-Resorcincalix[4]pyrrole extractant : A Newly Designed Collector for Selective Preconcentration of U(VI) and Th(IV) from aqueous solutions and their final Determination by inductively coupled plasma atomic emission spectrometric determination Vinod K. Jain* and Hrishikesh S. Gupte (Communicated) An efficient one pot Synthesis of Water-dispersible calixaryl acylhydrazine- protected gold nanoparticles- A “Turn Off” fluorescent sensor for Hg[II] ions Disha J. Vyas, Hrishikesh S. Gupte, Bharat A. Makwana, Keyur D. Bhatt, and Vinod K Jain* (Under process) Calix receptor edifice; Scrupulous turn off fluorescent sensor for Fe[III] and Co[II] Keyur D. Bhatt, Hrishikesh S. Gupte, Bharat A. Makwana, Disha J. Vyas, and Vinod K Jain* (Under process)

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