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A Study on Green synthesis and Optical properties of Nanoparticles using herbs plant extracts

D.Vijayakumar*, Dr.P.Prakash** and Dr.L.Selvarajan***

*Research Scholar, Department of Bio Engineering, Sathyabama Institute of Science & Technology,
Chennai-119 Tamilnadu.

*Corresponding author- biovijayakumar@gmail.com Mobile Number: 9994301462.


**Assistant Professor, Department of Bio Engineering, Sathyabama Institute of Science & Technology,
Chennai-119 Tamilnadu.
***Professor, Department of Mechanical Engineering, Mahendra Institute of Technology,
Mallasamudram, Namakkal, Tamilnadu.

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ABSTRACT

Aim: Green synthesis of nanoparticles makes use of environmental eco- friendly, non toxic
and safe reagents. Green synthesis aims in particular at decreasing the usage of toxic
chemicals.Nanoparticles synthesized using biological techniques or green technology have
diverse natures, with greater stability and appropriate dimensions since they are synthesized
using single step procedure. Therefore, plant extracts in green synthesis were found to be
ideal candidates for synthesizing metal nanoparticles due to their rapid growth, non-
pathogenic and eco-friendly reaction conditions that occur in a single step using a highly
economical protocol. This metallic nanoparticles green synthesized using diverse medicinal
plants have shown the most important therapeutic properties,such as antiliver cancer activity,
antimicrobial activity, antioxidant activity, wound healing properties, immunomodulatory
activity, hepatoprotective activity. Methodology: In our study, the extract of various parts of
green plants such as leaves, flowers, seeds, barks, fruits, and roots have been applied for
synthesis of metal nanoparticles and the plant extracts may serve as stabilizing and reducing
agents in the synthesis process. In producing nanoparticles using plant extracts, the extract is
simply mixed with a solution of the metal salt at room temperature. The reaction is complete
within minutes. Here, nanoparticles of TiO2, SeO and many other metals have been produced
also in this way. Metallic nanoparticles present an enhanced light scattering cross-section.
This characteristic is dependant on the size of the nanoparticle, and studies have found that in
particles that are smaller than 15nm, absorption overtakes scattering; whereas this effect is
the opposite in larger nanoparticles. Results: In this present study, we examined the use of
green plant extracts as a mediating agent for the green synthesis of metal-based nanoparticles
(MNPs). Further more, the optical properties have also been studied by photoluminescence
(PL) that indicates the formation of oxygen vacancies and self-trapped excitons in the
material. The samples showed the enhanced photocatalytic property. Interpretation: In this
study, we highlighted the exploration of the plant systems as the potential nanofactories has
wide interest in the biological synthesis of nanoparticles.

Graphical Abstract

Keywords: MNPs, TiO2, SeO and PL.

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1. Introduction:

Green synthesis of nanomaterials refers to the synthesis of different metal nanoparticles


using bioactive agents includes plant materials, microorganisms, and various biowastes
including vegetable waste, fruit peel waste, eggshell, agricultural waste (Narayanan KB et al.
2011).Plants are known as chemical factories of nature which are cost-efficient and need little
maintenance.Plants are increasingly being used to synthesize nanoparticles because of their
widespread availability, low cost, environmental friendliness, and non-toxic nature.The
enzymes present in leaf extract combines withTiO2 ions to form an enzyme substrate complex
with a charge transfer between quercetin and Ti resulting into formation of protein capped Ti
nanoparticles(Nath D et al. 2013). In nanoparticle synthesis, the part of the plant were washed
and boiled with distilled water. After squeezing, filtering, and adding respective solutions
which nanoparticles we want to synthesize, solution color starts changing unveiled the
formation of nanoparticles and we can separate these compounds. (DerPharmacia
Lettre, 2016).This study suggested that accumulation, detoxifcation, and phytoremediation of
toxic metals by some plants, such as Thlaspi caerulescens, Maytenus founieri, Arabidopsis
helleri (Pal G et al. 2019). The use of these plants in heavy metal elimination from aqueous
solutions has gained considerable attention due to its great potential for the removal of
pollutants and toxicity from wastes in an eco-friendly method (Environmental
Research, 2023).Many nanoparticles such as Ti, gold, silver, zinc oxide, iron have been
synthesized very easily by adopting a green approach (Islam NU et al.2019).

Study of Literature review:

T. Pushpamalini. et al. (2021)


Comparative analysis of green synthesis of TiO 2 nanoparticles using four different leaf
extract. Volume 40, Supplement 1, 2021, Pages S180-S184.Green synthesis of nano materials
has gained a great attention of current researchers owing to its less toxicity, reproducibility,
pollution free, economic and low energy process. Green synthesis of Titanium dioxide
(TiO2) nanoparticle was carried out using four different leaf extracts. The leaf extracts
of Piper betel, Ocimum tenuiflorum, Moringa oleifera, Coriandrum sativum were used as
reducing agents to synthesize TiO2 from Titanium tetraisopropoxide. The synthesized
TiO2 nanoparticle was then characterized by X-Ray Diffraction (XRD), Fourier Transform-
Infrared Spectroscopy (FT-IR), Transmission Electron Microscopy (TEM) and Scanning
Electron Microscopy (SEM) techniques. The spectroscopic and microscopic techniques
confirmed the formation, size and shape of the TiO 2 nano particle. Further the differences in
physical and morphological characteristics of synthesized nanoparticle incurred with the
different with the usage of different leaf extract was analyzed and justified. The differences in
the photocatalytic efficiency of synthesized TiO 2 nanoparticles were studied by degrading
Malachite green dye. Out of the four dyenanomaterials used, TiO 2 synthesized using Moringa
oleifera leaf extract.

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Yun Sun. et al.(2019)

Biosynthesis of TiO2 nanoparticles and their application for treatment of brain injury-An in-
vitro toxicity study towards central nervous system. Volume 194, May 2019, Pages 1-5. In
the current study, a facile green synthesis of TiO2 nanoparticles (NPs) utilizing the leaf
extract of Lippia citriodora as a stabilizing and reducing agent was reported. The prepared
TiO2 NPs were studied using XRD, UV, HRTEM, FTIR, Raman and EDS analysis. TEM
analysis confirmed that the nanoparticles size is in 20–40 nm range. FTIR and UV–Visible
spectra represented the TiO2 NPs formation. Similarly, the analysis of XRD and EDS
validated the crystalline rutile structure of TiO2NPs formed. In addition, this investigation
was shown to examine the TiO2NPs toxicity on the CNS central nervous system in vitro. In
the extracted cell cultures from the rats ECB embryonic cortical brain, substantial decline in
the neuroblasts has been noticed once after incubating with TiO2NPs for 24 h to 96 h (5 to
20 μg/ml). This study also demonstrates the decline of neuroblast proliferation.

Shilpa Hiremath. et al. (2013)

Green synthesis of ZnO nanoparticles by Calotropis Gigantea. Present study focuses on the
green synthesis of ZnO nanoparticles by zinc nitrate and utilizing the bio components of
leaves extract of Calotropis Gigantea. The ZnO nano crystallites of average size range of 30-
35 nm have been synthesized by rapid, simple and ecofriendly method. Zinc nanoparticles
were characterized using scanning electron microscopy (SEM) and X-ray diffraction (XRD).
The particles obtained are spherical in nature and are agglomerates of nanocrystallite. The X
ray patterns show hexagonal crystal type for ZnO. The results coincide with literature XRD
pattern for hexagonal wurtzite ZnO. The size of nano crystallites is calculated by considering
XRD data by DebyeScherrer’s Formula.

2. Materials and Methods:

Extraction of biologically produced metal nanoparticles:

Nanoparticles can be synthesized by leaves of plants where parts of plants are thoroughly
washed with the help of tap water and sterilized by double-distilled water followed by drying
at room temperature (Zangeneh Mmet al. 2020). Then,dried sample were weighed and
crushed. Afterward, plants extract is mixed with Milli-Q H 2O as per desired concentration
and boiled with continuous stirring. The obtained solution is then filtered with Whatman filter
paper, and the part in which there is a clear solution was useful for sample (plant extract)
(Wang et al. 2019).

3. Results and Discussion:

A. Preparation of nanoparticles by characterization methods:

In this study, nanoparticles are prepared by green technology and these particles were
characterized by ultraviolet–visible spectroscopy, Fourier transform infrared spectroscopy
(FTIR), Raman spectroscopy, Photoluminescence analysis (PL), Transmission electron
microscopy (TEM), Scanning electron microscopy (SEM), Energy dispersion analysis of X-

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ray (EDAX), X-ray diffractometer (XRD), Atomic force microscopy (AFM), Field emission
scanning electron microscopy (FE-SEM), thermal-gravimetric differential thermal analysis
(TG-DTA), X-ray photoelectron microscopy (XPS), Attenuated total reflection (ATR),
Dynamic light scattering (DLS) and UV–visible diffuse reflectance spectroscopy (UV-DRS)
(Jeyarani S et al. 2020).

(i) Analysis of Scanning Electron Microscopy (SEM): (ii) Analysis of X-ray diffraction (XRD)

Counts
TIO2NPS

1000

500

0
10 20 30 40 50 60 70 80
Position [°2Theta] (Copper (Cu))

Fig 1 : ×3,000 magnification Fig 2 : ×10,000 magnification Fig 3: TiO2 nanostructure patteren of X-ray diffraction

(iii) Analysis of Fourier Transform Infrared Spectroscopy (FTIR):


100

3855.39cm-1 1035.83cm-1
90 1384.87cm-1
2852.97cm-1 1637.37cm-1
2924.25cm-1 1453.11cm-1
80 3418.59cm-1

70

60

50
%T

687.13cm-1

40

30

20

10

0
4000 3500 3000 2500 2000 1500 1000 500 400
cm-1
Name Description
IR-Tio2NPS-

Fig 4: TiO2 nanostructure patteren of Fourier Transform Infrared Spectroscopy.

Green synthesis of TiO2 nanoparticles from plants is a better choice for toxic-free synthesis.
Many plants have been used for its synthesis and applications (Iravani S et al. 2011). In our
study, the green synthesis starts with the reaction of a plant extract with metallic salt.
Initially, preparation of nanoparticle can be confirmed by the change in color of the reaction
mixture, afterward that the morphological and spectroscopic studies confirmed their
formation (Rajkumar T et al. 2019). These nanoparticles are appear in light green to dark
green color. TiO2 nanoparticles in spherical shape were synthesized by this
method(Mohanpuria P et al. 2008).The reason for choosing mainly leaf extracts to synthesize
TiO2 nanoparticles is leaf extracts are always a rich source of metabolites (Sethy NK et al.
2020). TiO2 nanoparticles were synthesized (Goutam et al. 2018) by leaf extract of Jatropha
curcas. Likewise, Catharanthus roseus leaf extract was used to synthesize 25–110 nm TiO2
nanoparticles with irregular morphologies. In the leaf extract, the presence of aliphatic
amines and alcohols was responsible for nanoparticle synthesis (Velayutham et al. 2012).
Irregular shaped and size of 100-nm TiO2 nanoparticles were synthesized by Moringa oleifera

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leaf extract having superior wound healing capability(ICANMEET 2013).Similarly, metal
nanoparticles were achieved in 6 h by using Calotropis gigantea leaf extract.These
nanoparticles revealed outstanding acaricidal activity against the larvae of Haemaphysalis
bispinosa and Rhipicephalus microplus (Marimuthu et al. 2013).

B. The optical properties of Nanoparticles:

Optical properties of nanomaterial such as absorption, transmission, reflection, and light


emission are dynamic and can be differ significantly from properties exhibited by the similar
materials(Ahmad W et al. 2020). The optical properties of nanoparticles depend on their
dimension and shape, where in the larger size of the nanoparticles, as well as proximity of the
nanoparticles lead to resonance peak shift in the optical spectrum(Anastas P et al. 2010).

Fig 5: Intensity Distribution of DLS (Dynamic Light Scattering)

C. Applications of green synthesized nanoparticles:

The green synthesized TiO2 nanoparticles have a wide area of applications such as tissue
engineering, sensing, imaging, disease diagnostics, production of surgical tools, treatment,
agriculture, and energy production, etc. (Balantrapu Ket al. 2009) TiO2 nanoparticles derived
by Hibiscus rosa sinensis exhibited excellent antimicrobial activity against both Gram-
positive and Gram-negative strains of bacteria (Duan H et al. 2015).Similarly, TiO2
nanoparticles are widely applicable in the degradation of various pollutants such as nitroarene
compounds and toxic dyes (Roopan SM et al. 2012). Their large surface area, recyclability is
a key feature to make it a heterogeneous catalyst ( Karthick Raja Namasivayam, S., Flora,
A.M.et al .2016).The reduction of dyes and pollutants by TiO2 nanoparticles have been
reported by various authors (Ghosh NS et al. 2020). These study represents the photocatalytic
mechanism and electron flow by photoexcitation which results in the degradation of various
dyes and pollutants (Singh T et al. 2019). TiO2 nanoparticles synthesized by green route were
also applied to testify for removal of chromium (Cr) and chemical oxygen demand (COD)
from secondary treated tannery waste water (Hulkoti NI et al.2014).About 76.48% removal
of Cr and 82.86% removal of COD from tannery waste water (TWW) were attained on
Parabolic Trough Reactor with the treatment using green synthesized TiO2 nanoparticles
(Goutam et al. 2018).

4. Conclusion:

Plant synthesis of nanoparticles has been the focused area analysis by researchers in the
previous year by adopting an eco-friendly approach (Sundrarajan M et al. 2011). Many
research has been carried out on the plant extract-mediated nanoparticles synthesis and their
potential applications in various fields due to their cost-effectiveness, nontoxic route, easy
availability, and environment-friendly nature. The use of plants for green synthesis of

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nanoparticles is an exciting and developing part of nanotechnology and has a noteworthy
effect on the environment toward sustainability and further development in the field of
nanoscience.The approaching expectations from the plant route of nanoparticles synthesis are
that the applications of these will grow exponentially, but there is a need to affair about the
long-term effects of these on animal and human being as well as accumulation of these in the
environment is a subject of worry which has to be resolved in future (Sunanda K et al 1998).

In this present study, they give the photoluminescent spectra and their characterization is
done using microscopic techniques(ThakkarKN et al. 2010). 1 D nanomaterial serves as the
smallest dimension for optical excitation. In the case of 1 D nanomaterials such as rods and
wires, the aspect ratio plays an important ratio. Varying the aspect arrangement varies the
absorption in the altered regions of the spectra. The shape and size additionally affect the
optical properties. From the photoluminescent spectra of indium-based nanowires, it was
assured that the emission maxima changes with the change in the diameter. Park and
coworkers have accept fabricated up angular aligned ZnO nanorods with an average diameter
between 40 and 150 nm. They observed a blue light emission with a wavelength of 440 nm
from n-ZnO film/nanorods.

5. Acknowledgements:

We acknowledge TRI-BIOTECH Trichy (District) for characterisation and optical studies.

6. Conflict of Interest:

The authors declare that “No conflict of interest”.

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