Synthesis of Silver Nanoparticles from Fish Scale Extract of Cyprinus carpio and its Decolorization Activity of Textile Dyes

Journal of Environmental Treatment Techniques

2020, Volume 8, Issue 3, Pages: 870-874

J. Environ. Treat. Tech.

ISSN: 2309-1185

Journal web link: http://www.jett.dormaj.com

Synthesis of Silver Nanoparticles from Fish Scale

Extract of Cyprinus carpio and its Decolorization

Activity of Textile Dyes

Bharathi Vadivelu , Arun Meyyazhagan , Sampathkumar Palanisamy , Vijaya Anand

Arumugam , Hesam Kamyab , Balamuralikrishnan Balasubramanian , Shreeshivadasan

Chelliapan , Krishna Kumar Yadav

Biological and Bioinformatics Research Centre, Trichy, Tamil Nadu, India

EuroEspes Biomedical Research Centre, Institute of Medical Science and Genomic Medicine, Corunna, Spain

Department of Chemistry and Biosciences, SASTRA Deemed University, Kumbakonum, Tamil Nadu, India

Department of Human Genetics and Molecular Biology, Bharathiar University, Coimbatore, Tamil Nadu, India

Engineering Department, Razak Faculty of Technology and Informatics ,Universiti Teknologi Malaysia Jalan sultan Yahya Petra 56100 Kuala Lumpur,

Malaysia

Department of Food Science and Biotechnology, College of Life Sciences, Sejong University, Seoul, South Korea

Institute of Environment and Development Studies, Bundelkhand University, Jhansi, 284128, India

Received: 10/01/2020

Accepted: 11/05/2020

Published: 20/09/2020

Abstract

There is an increasing commercial demand for nanoparticles due to their wide applicability in various areas such as electronics,

catalysis, chemistry, energy, and medicine. This work deals with the synthesis and characterization of silver nanoparticles (AgNPs) using

Cyprinus carpio fish scale extract to de-colorization of textile dyes. The synthesized nanoparticles were characterized by using UV-Vis

absorption spectroscopy, FT-IR and SEM analysis. The reaction mixture turned to a brownish gray color after 5 hrs of incubation and

exhibits an absorbance peak around 450 nm characteristic of AgNPs. The SEM analysis showed AgNPs were pure and polydisperse and

the size were ranging from 200 nm. The approach of biosynthesis seems to be cost efficient, ecofriendly and easy alternative to

conventional methods of AgNPs synthesis. Dye degrading efficiency of AgNPs was assayed against azo dyes. At the end of 24 hrs AgNPs

showed 48.38% of degradation. As the days of incubation increases from 1 day to 7 days, the degradation efficiency was also increased

from 48.38% to 93.54% at the end of 7 day of incubation. Further, the FT-IR results confirmed that, the complex, toxic azo dyes are

degraded into simple, non-toxic compounds.

Keywords: Fish scale, Cyprinus carpio, Silver nanoparticle, Textile dye, Decolorization

an important aspect of nanotechnology. Their capability to reach

Introduction¹

high biomass and their feeding nature has been occupied in

causing major environmental poverty in several freshwater

ecosystems. The AgNPs are between 1 nm and 100 nm in size

Common carp (Cyprinus carpio) is considered to be a very

important aquaculture species in many Asian and some

European countries. C. carpio is an exotic fish species in India.

The C. carpio is usually considered to be one of the

most ecologically damaging fish species of all freshwater

bodies. The synthesis of silver nanoparticles (AgNPs) is

extensively studied by using biological methods, but the

development of reliable technology to produce nanoparticles is

has many applications due to

large degree of

commercialization. It is an attractive material for its distinctive

properties, such as good conductivity, chemical stability [1-3].

Textile dyes are complex unsaturated aromatic compound

that possesses characters like intensive color formation,

solubility, and fastness (fading property). In the early days, dyes

were used which was produced from natural sources. Azo dyes

are the most important group of synthetic colorants

characterized by the presence of one or more azo group (-N=N-).

They are the most versatile class of dyes and constitute 60% of

the dyes annually produced [4]. The effluents from textile

industries are complex, containing a wide variety of dyes and

other products, such as dispersants, acids, bases, salts,

detergents, humectants, oxidants, etc. Discharge of these colored

Corresponding authors: (a) Vijaya Anand Arumugam,

Department of Human Genetics and Molecular Biology,

Bharathiar University, Coimbatore, Tamil Nadu, India. E-mail:

avamiet@yahoo.com. (b) Dr. Hesam Kamyab, Engineering

Department, Razak Faculty of Technology and Informatics

Universiti Teknologi Malaysia Jalan sultan Yahya Petra 56100

Kuala Lumpur. E-mail: hesam_kamyab@yahoo.com.

Journal of Environmental Treatment Techniques

2020, Volume 8, Issue 3, Pages: 870-874

effluents into rivers and lakes results in reduced dissolved

oxygen concentration, thus creating anoxic conditions that are

lethal to resident organisms. The mechanism of microbial

degradation of azo dyes involves the reductive cleavage of azo

bonds (-N=N-) with the help of azo reductase under anaerobic

conditions involves a transfer of four-electrons (reducing

equivalents), which proceeds through two stages at the azo

linkage and in each stage two electrons are transferred to the azo

dye, which acts as a final electron. The resulting intermediate

metabolites (e.g., aromatic amines) are further degraded

aerobically or anaerobically. Thus, in the presence of oxygen

usually inhibits the azo bond reduction activity since aerobic

respiration may dominate utilization of NADH; thus impeding

the electron transfer from NADH to azo bonds. The potential

toxicity, mutagenicity, and carcinogenicity of such compounds

are well documented and have been reviewed elsewhere [5].

Therefore, the aim of this study synthesis and characterization of

AgNPs from C. carpio fish scale extracts and to evaluate the

activity on de-colorization of textile dyes.

evaluate the photocatalytic degradation of dye. The absorbance

spectrum of the supernatant was subsequently measured using

UV-Vis spectrophotometer at the different wavelength.

Concentration of dye during degradation was calculated by the

absorbance value at 590 nm [6].

Results and Discussion

The present study was carried out of preparation of

AgNPs from the fish scale extract of C. carpio. We developed a

simple protocol for synthesis and characterization of AgNPs

from the fish scale extract of C. carpio and studied the presents

of bioactive compounds. About 10% of the fish scale extracts

were mixed with silver nitrate solution in 1:9 proportions and

kept at room temperature for 72 hrs for the development of

reddish-brown color (Table 1). But in our investigation, the

AgNPs usually exhibited reddish brown color in aqueous

solution, due to excitation of surface plasmon resonance in the

AgNPs after incubation [7]. The appearance of reddish-brown

color in the reaction vessels suggested the formation of AgNPs.

Silver nitrate is used as reducing agents as silver has an identical

property such as good conductivity, catalytic and chemical

stability.

Materials and Methods

.1 Synthesis of silver nanoparticles

The fish scale sample collected from C. carpio. The fish

Table 1: Indication of Color Change for synthesis of AgNPs

scale samples are sun dried for 3 days, grind the sample and

used for the synthesis of AgNPs. To take 10g of fish scale

powder was mixed with 100ml of distilled water, then boiled

water bath at 70⁰C in 20 minutes. After cooling few minutes, to

filter by using Whattman filter paper get the fish scale extract.

After, prepared 100ml of silver nitrate solution. Added the scale

extract + silver nitrate solution (1:9) ratio. Incubate at dark

condition for 72 hrs. After, 3 days color changing of reddish-

brown color sedimentation formed (AgNPs).

.2 Characterizarion of silver nanoparticles

After the synthesis of AgNPs, the synthesized AgNPs are

taken for centrifugation at 6000 rpm for 15 mines. After

centrifugation the supernatant and pellet were collected. The

pellet was re-dispersed in deionized water to get uncoordinated

biological molecules. The supernatant was collected and stored

in refrigerator for further use. The pellet is airs dried for 24

hours and powdered from AgNPs are taken into Eppendorf tube

to undergo SEM analysis. The FT-IR Spectra of the sample

were recorded in order to Characterization the presence of

functional groups in isolated stains. All the measurements were

carried out in the range of 100-1000.

The reduction of silver metal ions to AgNPs was

preliminarily analyzed using UV-Vis Spectrophotometer

between 200-1000nm (Table 2 and Fig. 1). This analysis showed

an absorbance peak at 218 nm which was specific for Ag

nanoparticles. The reaction mixture changes the color by adding

various concentrations of metal ions. These color changes arise

because of the excitation of surface plasma vibrations in the

AgNPs.

.3 Photocatalytic degradation of dye

Typically, Azo dye was added to 1000 mL of double

distilled water used as a stock solution. About 10 mg of

biosynthesized AgNPs was added to 100 mL of Azo dye

solution. A control was also maintained without the addition of

AgNPs. Before exposing to irradiation, the reaction suspension

was well mixed by being magnetically stirred for 30 min to

clearly make the equilibrium of the working solution.

Afterwards, the dispersion was put under the sunlight and

monitored from morning to evening sunset. At specific time

intervals, aliquots of 2-3 mL suspension was filtered and used to

Table 2: Represents the corresponding UV-VIS absorption

spectrum of AgNPs

Wavelength

18.05

751.55

Absorbance

4.0000

0.2371

0.2581

37.20

Journal of Environmental Treatment Techniques

2020, Volume 8, Issue 3, Pages: 870-874

Figure 1: Represents the corresponding UV-VIS absorption spectrum of AgNPs recorded (1:9)

100

854.50cm-1

802.45cm-1

3745.74cm-1

64.20cm-1

06.50cm-1

69.70cm-1

71.75cm-1617.87cm-1

78.13cm-1

322.98cm-1

- 1

005.60cm-1

2855.15cm-1

2080.18cm-1

1317.00cm-1

952.55cm-1

1140.05cm-1

1077.02cm-1

1103.61cm-1

923.92cm-1

1405.07cm-1

437.13cm-1

357.73cm-1

646.63cm-1

1018.81cm-1

000

3500

3000

2500

2000

1500

1000

500 400

cm-1

Name

Description

Figure 2: FT-IR analysis spectra of AgNPs showed various transmission peats (1:9) ratio

cm ¹and 578.13 cm

̄ ¹

respectively (Table 3 and Fig. 2). Fig. 3

It shows yellowish to dark brown in color. The dark brown

color of silver colloid is accepted to surface plasma resonance

SPR) arising due to the group of free conduction electrons

showed that the AgNPs are spherical, triangular, rectangular and

cubical in shape with uniform distribution. However, no most

occasions; agglomeration of the particles was observed probably

due to the presence of the weak capping agent which moderately

stabilized the nanoparticles. Also, reveals the presences of

agglomerated nanoparticles were in the range 150.72 -200.49

nm; however, the average size of an individual particle is

estimated to be 200nm (Fig. 3).

(

induced by an interacting electromagnetic field. The FT-IR

spectra show the biosynthesized AgNPs and carried out to

possible interactions between protein and AgNPs. The result of

FT-IR analysis of SNP is presented in Fig. 2 spectra of AgNPs

showed transmission peaks at 3854.50 cm

, 3357.73 cm

, and

1 1 1

005.60 cm ̄ , 2923.92 cm ̄ , 1646.63 cm ̄ , 771.75cm , 669.70

̄ 1

Journal of Environmental Treatment Techniques

2020, Volume 8, Issue 3, Pages: 870-874

Table 3: Compound group and frequencies (1:9) ratio

Dye degradation was initially identified by color change.

Initially, the color of dye shows deep pink color changed into

light pink after the 1h of incubation with AgNPs while exposed

Group frequency (cm ^-¹

)

Functional group

solar

light.

The

degradation

was

analyzed

854.50 cm

̄ ¹

Primary amines

Carbonyl group (open-chain

acid anhydride)

spectrophotometrically. At every 24 hrs intervals sample was

derived and analyzed spectrophotometrically. The control

showed 0.31 Optical Density (OD). At the end of 24 hrs 48.38%

of degradation. As the days of incubation increases from 1 day

357.73 cm _̄1

005.60cm _̄1

Amide Group

to 7 days, the degradation efficiency was also increased from i.e.

923.92 cm

646.63 cm

̄ ¹

Trimethyl

8.38% to 93.54% at the end of 7 day of incubation (Table 4

Methyl C-H Group

Disulfides

and Fig. 4).

71.75cm

Table 4: Dye degradation efficiency of synthesized silver

69.70 cm

78.13 cm

nanoparticles

Absorbance after

photocatalytic

degradation (590

nm)

Aryl disulfides

Degradation

efficiency

Days of

Incubation (OD)

Initial

(

0.31

0.16

48.38

0.31

0.13

0.08

0.07

58.06

74.19

77.41

0.31

0.05

0.03

0.02

83.87

90.32

93.54

.31

0.31

During degradation the catalysis was occurring on the

surface region of metals, therefore increasing the surface area

availability will significantly improve the efficiency of the

catalyst. Decreasing the particle size will increase the catalytic

activity, but there is a critical size below which proves that

further decreases will actually hamper the reaction. Metal

nanoparticles support the electron (e-) relay from the donor to

the acceptor and act as a substrate for the e- transfer reaction.

During an e-transfer reaction, the reactants are adsorbed on the

surface of the metal and consequently, the reactants gain an e-

and are reduced. Thus, AgNPs act as an efficient catalyst

through the electron transfer process in all the above catalytic

reactions [8]. Table 5 and Table 6 showed the FT-IR spectrum

of control and samples obtained after decolorization of both dyes

showed various peaks. The appearance of some new peaks and

absence of important peaks in incubation with AgNPs while

exposed to solar light of the dyes have been observed in the FT-

IR analysis of the metabolites produced after decolorization. A

Figure 3: SEM of synthesized (1:9) silver nanoparticles

The SEM images show AgNPs were spherical and

polydisperse. Immobilization of Ag NPs on polymer films using

fish scale extract and was characterized by UV-Vis

spectroscopy, FT-IR and SEM. Recently, both academic and

industrial research has explored the possibility of using AgNPs

as a next generation anticancer therapeutic agent, due to the

conventional side effects of chemo and radiation therapy.

Although AgNPs play an important role in clinical research,

several factors need to be considered, including source of raw

materials, the method of production, stability, bio distribution,

controlled release, and finally toxicological issues of human

beings. We report a simple, facile, inexpensive, eco-friendly and

green synthesis of AgNPs from the fish scale extract without

employing man-made chemicals. The UV-Vis spectroscopy and

FT-IR analysis is confirmed the preliminary confirmation of the

formation of AgNPs. SEM image showed the spherical shape

with an average particle size of 200 nm. The biosynthesized

AgNPs from the fish scale extract of C. carpio showed

promising dye degrading efficiency. Dye degrading efficiency of

AgNPs isolated from plant extract was assayed against azo dye.

At the end of 24 hrs nanoparticles of the fish scale extract

showed 48.38% of degradation. As the days of incubation

increases from 1 day to 7 days, the degradation efficiency was

also increased from i.e. 48.38% to 93.54% at the end of 7th day

of incubation. The FT-IR results confirmed that, the complex,

toxic azo dyes are degraded into simple, non toxic compounds.

In the current investigation, fabric azo dyes were

new peak at 1384 cm represented -N=N- stretching vibration.

The C-H deformation showed at 1112 cm . The peak at 1384

cm showed N-H stretching vibration. The significant change in

the FT-IR spectrum of metabolites compared to control

spectrum suggests the biotransformation of complex dyes

present in the mixture into simple form. The FT-IR spectrum

of control dye 6 displays peaks at 3449 for intramolecular

hydrogen bonding and O-H stretches. Peaks in the control dye

spectrum represented symmetric stretching at 1384 cm and

asymmetric stretching at 1114 cm for C-N. C-N stretching at

1637 cm represented nature of the aromatic amine group

-1

present in parent dye; 3449 cm and 2075 cm represented the

presence of a free NH group of parent dye. Whereas peak at

-1

1637 cm represented -N=N- stretching of azo group. In

-1

collected from Tiruppur, Tamilnadu, South India, and

decolorized by AgNPs isolated from C. carpio under solar light.

degraded extracted metabolites, a new peak at 435 cm

Journal of Environmental Treatment Techniques

2020, Volume 8, Issue 3, Pages: 870-874

represented C-H deformation of alicyclic CH

whereas a peak at

2. Gong P, Li H, He X, Wang K, Hu J, Tan W, Zhang S, Yang X.

Preparation and antibacterial activity of Fe O Ag nanoparticles.

85 cm was observed for substituting anilines. The FT-IR

Nanotechnology. 2007;18:p. 604-611.

3. Aminiranjbar GH. Heavy metal concentration in surficial sediments

from Anzali wetland, Iran. Journal of Water Air and Soil Pollution.

analysis result of peak at 3375.38 cm indicates primary amides,

the peaks at 1789.9 cm indicates carbonyl Group, the peaks at

639.78 cm indicates amide Group.

998;104 (4):p. 305-312.

. Russ R, Rau J, Stolz A. The function of cytoplasmic flavin reductases

Table 5: The FT-IR spectrum of control dyes

in the reduction of azo dye. Int. J Chem. 2000;66(4):p.1429-34.

. Chung KT, Cerniglia CE. Mutagenicity of azo dyes: structure- activity

relationships. Mutation Res. 1992; 277(3):p.201-220.

. Guzman MG, Dille J, Godet S. Synthesis of silver nanoparticles by

FREQUENCY

RANGE

TYPE AND

GROUP

TYPE OF BOND

chemical reduction method and their antibacterial activity. World Acad.

Sci. Eng. Technol. 2008;43:p.357-364.

459

080

638

O-H Stretch- H Bonded

-C=C- Stretch

Alcohols, phenols

Alkynes

. Karcher S, Kornmuller A, Jekel M. Screening of commercial sorbents

for the removal of reactive dyes. Dye and Pigment. 2001; 51:p.111-125.

. Duran N, Marcato PD, Conti RD, Alves OL, Costa FTM, Brocchi M.

N-H bend

1^oamines

384

C-H bend

Alkanes

Alkyl halides

Potential use of silver nanoparticles on pathogenic bacteria, their toxicity

and possible mechanisms of action, J. Braz. Chem. Soc. 2010;

C - Br Stretch

1(6):p.949-959.

Table 6: The FT-IR spectrum of samples obtained after

decolorization of dyes

FREQUENCY

RANGE

TYPE AND

GROUP

TYPE OF BOND

O-H Stretch-H

449

075

638

Alcohols, phenols

Alkynes

Bonded

-C=C- Stretch

N-H bend

1^oamines

C - Br Stretch

Alkyl halides

Conclusion

To conclude, this is an efficient, eco-friendly and simple

process. The nanoparticles were found to be active in degrading

azo dye solution with visible light illumination. These findings

suggest that AgNPs synthesized by facile method from plant

extract are able to degrade dyes in the presence of visible light

and pave way for ecological health and environmental

bioremediation. Similarly, instead of using hazardous, time

consuming and costly chemicals, we could protect our

environment from dyes by using these types of natural AgNPs

isolated from fish extract. The present study, it is found that the

use of natural, renewable, and eco-friendly, reducing agent used

for synthesis of AgNPs exhibits excellent photocatalytic activity

against dye molecules and can be used in water purification

systems and dye effluent treatment.

Acknowledgment

This research work was acknowledged by Universiti

Teknologi Malaysia under the Research University Grant, Vote

Number: Q. K130000.2510.13H11. Hesam Kamyab is

researcher of Universiti Teknologi Malaysia (UTM) under the

Post-Doctoral Fellowship Scheme (PDRU Grant) for the project:

“Alternative Innovation of Enhancement Technologies for Algal

Oil Extraction” (Vote No. Q. J130000.21A2.03E31) and

Enhancing the Lipid Growth in Algae Cultivation for Biodiesel

Production.

References

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carpio: from Roman gourmets to the swimming flowers. Aquaculture.

995;129(1-4):p. 3-48.