MTOE17 – Nano-materials and Applications

Project Title: Green Synthesis of Nano-materials

PROJECT MEMBERS:

SADHANA.S 112116048

ANUSHA.A 112116007

SIVASRI 112116032

PARVESH 111116035

RAJ KISHORE 112117036

SREENATH 112113049

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 INDEX

1. Introduction………………………………………………………………3
2. Properties………………………………………………………………….3
3. Unique characteristics……………………………………………………....4
4. Applications………………………………………………………………..5
5. Synthesis Methods……………………………………………………….....6
6. Conventional Green methods……………………………………………....8
7. Challenges and limitations …………………………………………………9
8. Advantages and Disadvantage……………………………………………...10

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INTRODUCTION
Nano-materials are of great importance in various sectors. Though their applications are encouraged worldwide
the method of their manufacturing creates a large quantity of waste thus highly environment damaging.
Environmental impact and sustainability analysis performed using E-Factor representing the waste to product
ratio.

Green nanotechnology is not merely initiating the next industrial scientific revolution but is also facilitating
technological solutions by developing new industrial and chemical methodologies. These new methodologies
will develop alternative replacement materials for hazardous processes and constituents, offering better
solutions to these problems, thus rightly reflecting the fact that safe nano is green nano.

The nanotechnology industry is increasingly promoting nano as a “green” technology that will improve the
environmental performance of existing industries, reduce consumption of resources and energy, and allow
achievement of environmentally benign economic expansion.

Eco-friendly solutions are gaining popularity in the contemporary world. A green method for nanoparticle
synthesis should be assessed.

FACTORS AND PROPERTIES GOVERNING;

The green synthesis of Nano-particles considers three major aspects:

1. The solvent,
2. the capping agent, and
3. reducing agent compared to physical and chemical methods.

The source for the process to begin is organic plants. The plant extracts mediated process is a good and
advantageous method for the development of metal nanoparticles compared to using microorganisms, in which
the cell maintenance time is limited.

Requirements for effective green synthesis process include,

Synthesis and characterization of nanoparticles are important steps to be adopted to apply nanoparticles in field
applications, and these steps include

1. Preparation of leaf extract,

2. Phytochemical screening, and
3. Preparation of precursor.

Example; Diatoms (Microalgea) produce nanostructured Biosilica, which is achieved by the use of amine
functionalized biomolecules. These biomolecules play a major role in Bio-mineral deposition both as a catalytic
agent facilitating the deposition itself and, through their compel self-assembling behavior at a range of length
scales, as a structure director of the resultant inorganic materials. [11]

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Generalized Limitations:
The degradation of any organic compounds by the green approach (plant extracts) is mainly due to the presence
of polyphenols in the biodegradable material.

1. The limited supply of biomolecules for the effective synthesis.

2. The prohibitive costs associated with process of synthesis.

Factors that govern the green synthesis of Nano-materials include pH, Temperature , Time .

UNIQUE CHARACTERISTICS

Synthesis of metal nanoparticles by green method is one of the best and environment friendly methods.
Biosynthesis of nanoparticles decreases the toxicity caused by the conventional method. Than conventional
processes, this method has proven to have fewer chances of failure, low cost and ease of characterization.

The chemical and physical method of synthesis of nanoparticles imposes several stresses on the environment
due to its toxic metabolites. Due to their exceptional properties, the green method has been favored by the
scientists rather than the conventional method.

The green synthesized nanoparticles also show significant biological activities such as, being active against
gram positive and gram negative bacteria, antifungalagainst Trichophytonsimii, Trichophytonmentagrophytes
and Trichophytonrubrum as well as different types of cancer cells such as breast cancer cell line, antioxidant
properties as well.

In dry methods, UV, lithography, and aerosol are not regarded as environment-friendly techniques. These lead
to the toxic materials to be retained on the surface of synthesized materials, which restrict their usage in the
biomedical, clinical applications. Thus an increasing tendency has been created to develop biocompatible
materials by environment-friendly routes. The green method also considers about the economical factors for
future usage. [12]

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APPLICATIONS

1. Drug delivery strategies using Au nano particle platforms: Drug transportation is one of the major
factors for producing efficient Drug Delivery system (DDS). Loaded nano-particles with drugs by non-
covalent bond interactions or maybe by conjugations making pro-drugs, which is administrated by the
cell. The gold nanoparticles offer an exceptional pathway for DDS strategy due to purposeful
adaptability of their monolayers. [5]

2. Hemolytic activity of Au nanoparticles: Biocompatibility and it should not produce any toxic effect
are the basic requirement of biogenically synthesized nanoparticle. The biocompatibility is mainly
related with the surface of the particle size and can be resolute based on the adversative host reaction
concentration. Au nanoparticles are non-toxic in nature, stable, inert and highly binding capability, so
due to this reason gold nanoparticles are used for anticancer drug carrier. These have no heamolytic
properties against red blood cells.

3. Waste water treatment by Fe based nanoparticles: Iron oxide nanoparticles synthesized using
Cynometraramiflora leaf extract. The antibacterial and catalytic activity of the iron oxide nanoparticles
was against E.coli, S. epidermidis and Rhodamine-B dye. The synthesized nanoparticles exhibited good
antibacterial activity against the pathogens and they have also achieved 100% degradation within 15
mins when 2% H2O2 and 1.11mM iron oxide nanoparticle. The synthesized iron oxide nanoparticles
can be effectively used in the field of wastewater treatment. [5]

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Synthesis methods:
Biological processes have recently been considered as possible methods for the synthesis of nanoparticles,
especially the development of “green” synthetic approaches for nanoparticles. The biosynthesis of silver
nanoparticles of different sizes, ranging from 1 to 70 nm, and shapes, including spherical, triangular, and
hexagonal, has been conducted using bacteria, fungi, plants, and plant extract.

In this study, the formation of silver nanoparticles was investigated using silver(I) nitrate in the presence of the
filamentous cyanobacterium .This organism was chosen in this study because cyanobacteria form one of the
largest and most important groups of photoautotrophic bacteria on earth.

(A) Precipitation of silver nanoparticles on the

cyanobacterial surface.

(B) TEM micrograph of a thin section of

cyanobacteria cells with nanoparticles of silver
deposited inside the cell.

(C) Spherical nanoparticles of silver

precipitated in solution.

(D) Spherical nanoparticles of silver

precipitated in solution.

Cyanobacteria Culture: The cyanobacterium, was grown in batch cultures at a control temperature of 29 °C
under ambient CO2 conditions. The pH of the medium was adjusted to 8.0 using a 1 M NaOH solution.

The cyanobacterial experiments were conducted to examine the role of cyanobacteria in the synthesis of silver
nanoparticles from aqueous solutions of AgNO3. The experiments were conducted at 25, 60, and 100 °C for up
to 28 days after the incubation period with silver solutions and maintained in the dark, and cyanobacteria
populations were measured with time.The effects of AgNO3 on the cyanobacteria were monitored during the
course of the cyanobacterial experiments.The pH was monitored using a Denver Instrument Basic pHmeter.

Transmission Electron Microscope (TEM):Thin sections of cyanobacteria and silver nanoparticles from the
experiments were examined with a transmission electron microscope (TEM) along with an energy-dispersive
X-ray spectrometer (EDS). The whole mounts were prepared and were then washed with distilled, deionized
water and allowed to air dry. Selected-area electron diffraction patterns of the precipitated solids were obtained
by TEM.

X-ray Photoelectron Spectroscopy (XPS). The reaction products obtained from the cyanobacterial
experiments using AgNO3 at 25 and 100 °C and day 28 were analysed by XPS to investigate the oxidation state
of silver and sulphur.

Cyanobacterial Experiment results: With the addition of AgNO3 to the cyanobacteria cultures, the soluble
silver concentrations kept ondecreasing until the end of experiments. At 100 °C, the soluble silver was
completely precipitated from solutions within 28 days. A greyish-black silver precipitate on cyanobacteria was

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observed macroscopically All cyanobacteria were killed within several hours at all temperatures investigated (25
to 100 °C). In abiotic experiments using AgNO3, total soluble silver concentrations were constant until the
completion of experiments at all temperatures investigated.

Green synthesis of nanoparticles using plant extracts;

Among metallic nanoparticles, silver nanoparticles are very important especially due to their physiochemical and
antimicrobial properties which help in therapies and devices used for medical procedures.

Procedure:

The fresh leaves of neem or conifer were collected. About 20 or 25gm of leaves were thoroughly washed with de-
ionized water to remove dust particles and air dried at room temperature. Then the leaves were finely chopped into
small pieces and added to 100 ml of deionized water, stirred for 20 min at 80ºC.

After boiling, the leaf extract was cooled at room temperature. The water turn greenish in colour and therefore it
indicates the formation of leaf extraction in water.

Pictures obtained from Refernces [4]

Now filter out the extract as the extract will be used as a Reducing and Capping agent. Now take 10mg of
SilverNitrate in 50ml of Deionized water and set the temperature to 60-70°C.

Addition of leaf extract to de ionized water until the light yellow colourforms.when the yellow colour appears the
silver nanoparticles in water is formed.

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Green synthesis versus conventional methods;

In today’s world, nanoparticles are being more frequently employed thus the search for newer methods also
increases. Some successful methods which has been in use for long are termed conventional methods, which
can be split majorly in two; [6]

Top Down Method: Includes Lithography, Milling, Etching etc.

Bottom up Method: Vapour deposition, Sol-Gel, Pyrolysis etc.

Problems faced in Conventional Methods

1) Sustainability poses the major problem, as toxic chemicals are produced as by-products.(Example: AuNP
nanoparticle synthesis involve a lot of toxic regents and carcinogenic solvents)

2) Efficiencies are poor where in each step in the process wastes are generated so overall quite a large amount
is produced in multiples. And in conventional methods, it is a fact that about 100000 kg of waste is produced
per kg of nanomaterials obtained.

3) These processes require ultrapure precursors which in turn require high energy for creation of these
precursors.

4) Requires high amount of water and energy, leading to depletion and unsustainability.

5) Some prove to be hazardous if mishandled (using of machinery and radiation)

6) Wet chemical methods form a major method, which use solvents that might be harmful. [6]

Green Synthesis: An answer to the above problems [3]

1) Biological components itself act as a reducing and capping agent therefore reduction of overall cost of
synthesis process. Fungi is an example where enzymes/reducing components on its cell surface itself.

2) External experimental conditions like high pressure and high energy is not required, leading to energy
saving process

3) Eco-friendly approach, as toxic chemicals are not used.

4) For synthesis of metal nanoparticles, plant extracts are used which are quite abundant and non-toxic, which
has effective phytochemicals such as ketones, amides used to break down the salts.

5) The one-pot solution: Plant extracts here can accommodate heavy metals in their diverse parts, so various
plants together can reduce and stabilize, leading to simple and cost-effective process.

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Challenges and Limitations of Green Synthesis;

Green synthesis methods have many advantages as seen, but it too has its own set of limitations and now at
present it is what we call as emerging state, with some challenges discussed as

1) Quality: Wastes are produced less, but the quality of the nanoparticle also matters, in which some process
compromise on quality, leading to performance issues.

2) Large scale manufacturing also poses a problem as these processes are now to say produces only limited
supply, which might not suit for industrial purposes. [7]

BioInspired: A synergy of Green and Traditional synthesis methods

This process aims to create a mean between both the processes, managing to get the best out of both worlds.
This involves understanding of the chemical reactions that occur in the biological synthesis and then designing
synthetic molecules for the purpose required. This helps to have the green nature and also a control over its
properties such as porosity. Usage of less hazardous chemicals and yet reduced time and energy usage, so thus
achieving the required products with less consequences.

Advantages:
Green synthesis of nanoparticles (NPs) or composites is preferred because of its cost effectiveness and
environmental compatibility(eco-friendly). The use of live organisms or safe applicability of environmentally
compatible process conditions is always lucrative for pharmaceutical and other biomedical applications. [8]

Plants:

It is cost effective and environmental friendly, ease in scaling up for larger production and it is straightforward
approach. Microorganisms can also be utilized to produce nanoparticle, but the rate of synthesis is slow and
only a limited number of sizes and shapes are amenable to the method compared to routes involving plant-based
materials. In the method of green synthesis, there is no requirement for high pressure, energy, temperature, or
toxic chemicals. Plants produce more stable nanoparticle compared to other means and it is very straightforward
to scale up. The risk of contamination is also lower. due to these advantages, green synthesis is gaining extreme
importance in all the fields focusing on a greener environment. iron nano particles can extracted from green tea
leaf.

Microorganisms;

Environmentally effective, affordable, cost-effective, and uniquely structured with a high capacity for metal
uptake while maintaining safety levels. They are environmentally friendly because the toxic chemicals produced
during the biosynthesis of the nanoparticles can be degraded with the help of enzymes present in the microbes

Microwave assisted technique;

An advantage of microwave irradiation over conventional biological synthesis is the improvement in rate
kinetics of the reaction due to the rapid heating and penetration involved, which may result in a narrow
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distribution of the particle size. Other advantages are (a) quick reaction, (b) simple medium, (c) short time to
reach a suitable temperature for reaction, and (d) control of its morphology of particles .

Microorganism-mediated technique:

Both extra- and intracellular nanoparticles can be synthesized by a variety of microorganisms. The group of
bacteria linked to different biogeochemical cycles, usually by different enzymatic actions, reduces the metallic
salts to its ionic form (e.g., nitrate reductase present in nitrogen cycle-linked bacteria). Extracellular synthesis
takes place during enzymatic action, and intracellular nanoparticle synthesis takes place employing bacteria by
macrophaging and reducting to a nanoform, which is further excreted or stored in vacuoles for further use or
disposal. Fungal nanoparticle synthesis is more advantageous due to its mycelial meshwork, fastidious growth
characteristics, and easy handling and fabrication.

Disadvantages:
Green synthesis methods have many advantages as seen, but it too has its own set of limitations and now at
present it is what we call as emerging state, with some challenges discussed as

1) Quality: Wastes are produced less, but the quality of the nanoparticle also matters, in which some process
compromise on quality, leading to performance issues.

2)Large scale manufacturing also poses a problem as these processes are now to say produces only limited
supply, which might not suit for industrial purposes. [10]

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Reference:

[1] Xianchun Zhu, ... Huey-Min Hwang, in Green Synthesis, Characterization and Applications of
Nanoparticles, 2019
https://www.sciencedirect.com/topics/engineering/green-synthesis

[2] BMC: Journal of Nanotechnology

https://jnanobiotechnology.biomedcentral.com/articles/10.1186/s12951-018-0408-4

[3] Green Chemical and Biological Synthesis of Nanoparticles and Their Biomedical Applications

doi:10.1007/978-3-319-15461-9_7

[4] Green Synthesized Iron and Iron Based Nanoparticle in Environmental and Biomedical Application –
A Review

doi:10.1049/iet-nbt.2018.5048

[5] Biomedical applications of green synthesized Nobel metal

nanoparticlesdoi:10.1016/j.jphotobiol.2017.05.034

[6] Science Direct: Bioinspired synthesis as a potential green method for the preparation of nanomaterials:
Opportunities and challenges - Siddharth V. Patwardhan

https://www.sciencedirect.com/science/article/pii/S2452223617300913#bbib11

[7] BMC: Journal of Nanotechnology

https://jnanobiotechnology.biomedcentral.com/articles/10.1186/s12951-018-0408-4

[8] ACS Sustainable Chemistry and Engineering.

https://pubs.acs.org/doi/pdf/10.1021/acssuschemeng.6b02121

[9]Kalidindi N, Nandeep R, Swetha S, Kalidindi B. Antifungal and antioxidant activities of organic and aqueous extracts
of Annona squamosa linn. Leaves. J Food Drug Anal. 2015;23:795–802. [PubMed] [Google Scholar]

https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5822509/

[10] https://link.springer.com/article/10.1007/s40097-018-0291-4

[11] ACS Sustainable Chemistry and Engineering

https://pubs.acs.org/doi/10.1021/la0613124

[12] Journal of NanoBioTechnology:

https://jnanobiotechnology.biomedcentral.com/articles/10.1186/s12951-018-0408-4#Sec9

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