Nano-medicine

1. Green sysnthesis of Metals and their Oxide
Nanoparticles: Application for Environmental
Remedation.
Dr Rai Dhirendra Prasad
Bihar Veterinary College, Patna,
India
Col Amit Sinha
SPPU, Pune, India
1

2. 2
PART I
What Is Nanotechnology?

3. “Nanotechnology is the art and science of
manipulating matter at the nanoscale”

4. Nanotechnology in Ancient Period
 Ras-Ratnakar: described the formation of metallic
nanoparticles about 5000 years ago
Shodhan: purification
Maran: killing the metallic properties
 Alchemist- Aurum potable & Luna potable about 1570
 Dr Samuel Hahnemann- Organon of medicines
 Lycurgus Cup: 4th century AD
4

5. History
The idea of nanotechnology
was born in December 29, 1959
when physicist “Richard Feynman”
gave a lecture exploring the idea
of building things at the atomic
and molecular scale. He is regarded as
Father of Nanotechnology and given the
Famous statement “There is plenty of
Room at the bottom”
He imagined the entire Encyclopedia
Britannica written on the head of a pin.

6. Nanoparticles
 "A particle with the size of the order of 1-nm to 100nm in
any dimension and at least any one property different
from that of bulk".
 During the synthesis of nanoparticles, size of nanoparticles
depends on the steochiometric ratio of metal ion to capping
ligands concentration.
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7. Properties at nanoscale
 Properties of nanoparticles: depend upon size, shape, stabilizing agent,
method of preparation etc.
 Changes in optical, thermal, electrical, electronic, magnetic and
mechanical properties
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8. Melting Point
 Graph of melting point (Tm)
vs size of particle (D)
 Melting point of nanoparticles
is below the melting point of
bulk material
Tm= TmBulk (1-1/D)
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9. Optical Property
 Size dependent optical
properties of
gold nanoparticles
 This effect appears due to the
interaction of electro-
magnetic radiation with the
electron cloud present on the
surface of metal
nanoparticles
9

10. Surface Plasmon Resonance
 Surface Plasmon
oscillations.
 Large number of atoms
present on the surface of
nanoparticles contributes
electron cloud which
interacts with E-field of
light and thus oscillates
10

11. Electronic Property
 When the size enters nano level, electron motion is
restricted to a smaller space, they don’t follow classical
theory & restricts themselves from diffusion of valence and
conduction band.
 The energy gap between valence band and conduction
bond (Kubo gap) becomes larger than thermal energy
(KBT) and hence metallic nanoparticles become
semiconductor further becomes an insulator
11

12. Other Properties
 Magnetic Property: Bulk materials forms multiple magnetic domains, but
nanoparticles form only a single magnetic domain thus could be used for
super magnetism.
 Bio-compatibility:
 Electrical Properties: The metals that are good conductance behave as
semiconductor at nano-level.
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13. Property changes…
 opaque substances become transparent (copper)
 stable materials turn combustible (aluminum)
 insoluble materials become soluble (gold)
 Chemically inert becomes active (Gold)
13

14. Why different property at Nanoscale
• High Surface to Volume ratio (Aspect ratio) : Because of this the
nanoparticle become less stable .
 Gravitational force: is not effective
 Size comparable to wavelength of light: thus entire different optical
properties like Surface Plasmon Resonance is exhibited.
 Dangling bonds:
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15. Surface to Volume Ratio
 spherical particle,
 surface area = 4πr2 and volume
= 4/3 π r3
 Sp= 4πr2σ/ (4/3)πr3ρ
 Where, σ is surface area factor and ρ is
volume factor
 r→o , Sp→∞
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16. Quantum mechanics
 Nanoparticles do not obey the laws of classical mechanics; instead they
follow the principles of quantum mechanics.
 Exhibits interesting shape dependence due to electronic motion in
different dimensions.
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17. Example of shape dependent property
 Electronic tunneling phenomenon is observed for 0-D
nanostructures which is the key concept used for building
artificial atoms and devices like single electron transistors.
 Electron can oscillate in two distinct ways in 1-D nanostructures
under electromagnetic field, namely in longitudinal and
transverse modes. The way electrons executes its motion alters
their various properties and thus nano-rods and nano-tubes
give rise to Surface Plasmon absorption peaks due to the two
different types of electronic motion.
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18. Nanoparticles as Smart Material:
 Smart materials are the materials that respond favorably to change in
temperature, pH, moisture or electromagnetic fields thus are extensively
used as sensors and actuators.
 Nanoparticles can also be used as advanced engineering materials which
can withstand high temp, high impact,
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19. Nano-composites
 Light weight Nano composites can replace heavy metals in automobile
industry to achieve high speed in vehicles
 Nano-composites are actively used to enhance the efficiency of solar cells,
and also in superconductor and super capacitors
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21. Norio Taniguchi
 The term "nanotechnology" was defined by Tokyo Science University
Professor Norio Taniguchi in a 1974 paper as follows: "'Nanotechnology'
mainly consists of the processing, separation, consolidation, and
deformation of materials by one atom or by one molecule."
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22. Stabilization of Nanoparticles
 Tendency to form agglomeration:
 Stabilizing agent: usually accomplished by suitable passivating agents also
called as capping agent.
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23. Gibb’s Free Energy & Stability
 As size of the nanoparticles decreases their surface energy
increases.
 Increase in the surface energy results in increase in the Gibb’s
free energy.
 According to the law of thermodynamics, every system always
tries to attain minimum Gibb’s free energy
 Therefore it loses its nanoness and exotic properties related to
it. Hence it is very important to stabilize the nanoparticles
against the aggregation.
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24. 24
Electrostatic Stabilization

25. Potential energy vs distance between the
nanoparticles
 Particles formed are surrounded by the electronic double
layer of reactant ions on the surface of nanoparticles
 Two forces: Van der Waals forces of attraction , and
electrostatic force of repulsion due to the charged ions on
the surface.
 Stability of nanoparticles is dependent on the combined
effect of these two forces.
 Greater the thickness of the double layer, higher is the
potential energy barrier & higher is stability
25

26. 26
Different Capping agents used for Surface Modification & Stabilization

27. Surface Modification using Capping Agent
 Electron rich ligands such as amines, thiols, phosphates, carboxylates
used for capping of nanoparticles
 Surface modifications like reactivity, Charge on the surface, specific
gravity, nature of surface i.e. hydrophobicity induced in the nanoparticles
with the help of different capping agents.
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28. 28
Stabilization by Steric interaction where Electrostatic Force of repulsion
are weak

29. Steric Interaction for Stabilization
 Nanoparticles dispersion in organic medium experiences
less significant electrostatic effects and stability comes from
steric interactions by adsorption of amphiphilic molecules.
 The lead group of these molecules binds with metal
nanoparticles surface while hydrocarbon chain prevents
aggregation sterically as shown in figure.
 Due to these steric interactions, the nanoparticles are
found to be stable in the form of powder even after
complete evaporation of solvent.
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30. Choice of Capping Agent
It determines:
 Stability
 Reactivity
 Size and shape
 e.g. Poly vinyl alcohol
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31. Synthesis Techniques
1) Bottom-up technique
2) Top- down technique

32. 32

33. Methodology
 Adopted method is Chemical route of synthesis and
Biosynthesis using plants
 Prepared nanoparticles characterized using different
characterization techniques
 Antimicrobial activity
 Synergetic effectiveness study
 Use of synthesized NPs for dye degradation reaction
 Use of synthesized NPs as potential catalyst in organic
transformation reaction
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34. PART II
Biosynthesis Of Nanoparticles

36. Why green synthesis?
 To avoid production of
unwanted/harmful by-products
 For reliable and cost-effective
build-ups
 For production of nanoparticles
at large-scale
 3 R’s (Reduce, Recycle, Reuse)
 Controlled morphologies
 Bio-compatible products

37. Biosynthesis:
• Production of chemical compounds
from precursors in living organism.
• Involves enzymes and energy
sources.
• some examples; photosynthesis,
chemosynthesis, amino acid
synthesis, nucleic acid synthesis,
and ATP synthesis.
• The biosynthesis method for
production of nanoparticles have
more effective applications than
physical and chemical synthesis
method, because this method is
reliable, nontoxic, and eco-friendly.
 Nanoparticles are biosynthesized
when the microorganisms grab
target ions from their environment
and then turn the metal ions into
the element metal through enzymes
generated by the cell activities.
 It can be classified into intracellular
and extracellular synthesis
according to the location where
nanoparticles are formed.
 The organisms used for synthesis of
nanoparticles are bacteria, fungi,
yeast.

39. 1. Bacteria:
 Bacterial species have been widely
utilized for commercial
biotechnological applications such as
bioremediation, genetic engineering,
and bioleaching.
 Bacteria possess the ability to reduce
metal ions and are momentous
candidates in nanoparticles
preparation . For the preparation of
metallic and other novel
nanoparticles, a variety of bacterial
species are utilized.
 Prokaryotic bacteria and
actinomycetes have been broadly
employed for synthesizing
metal/metal oxide nanoparticles.
2. Fungi:
 Fungi-mediated biosynthesis of
metal/metal oxide nanoparticles is also a
very efficient process for the generation
of monodispersed nanoparticles with
well-defined morphologies.
 They act as better biological agents for
the preparation of metal and metal oxide
nanoparticles, due to the presence of a
variety of intracellular enzyme .
 Competent fungi can synthesize larger
amounts of nanoparticles compared to
bacteria. Moreover, fungi have many
merits over other organisms due to the
presence of enzymes/proteins/reducing
components on their cell surfaces.
 The probable mechanism for the
formation of the metallic nanoparticles
is enzymatic reduction (reductase) in
the cell wall or inside the fungal cell.

40. 3. Yeasts:
 Yeasts are single-celled
microorganisms present in
eukaryotic cells. A total of 1500 yeast
species have been identified.
 Successful synthesis of
nanoparticles/nanomaterials via
yeast has been reported by
numerous research groups.
 The biosynthesis of silver and gold
nanoparticles by a silver-tolerant
yeast strain and Saccharomyces
cerevisiae broth has been reported.
4. Plants:
• Plants have the potential to accumulate
certain amounts of heavy metals in their
diverse parts. Consequently, biosynthesis
techniques employing plant extracts have
gained increased consideration as a simple,
efficient, cost effective and feasible methods
as well as an excellent alternative means to
conventional preparation methods for
nanoparticle production.
• There are various plants that can be utilized
to reduce and stabilize the metallic
nanoparticles in “one-pot” synthesis
process.
• Many researchers have employed green
synthesis process for preparation of
metal/metal oxide nanoparticles via plant
leaf extracts to further explore their various
applications.

41. Green synthesis of silver nanoparticles
using Gongura leaf extract

42. PART III
Uses of Nanoparticles

43. Ayurveda and Unani uses of nanoparticles :
 In Sanskrit, Ayurveda means ‘ the science of life ’.
 Ayurveda is the oldest form of Indian traditional system of
medicine. The other traditional system of Indian medicine
includes Unani and Siddha.
 Ayurveda aims at strengthening the capacity of the body and
improving immunity by using herbs and minerals in its
medicines.
 whereas Unani, which is the holistic system of medicine, is
quite common throughout the India.
 A section of Ayurveda deals with herbo-mineral preparations
called Bhasma (ash) is known as Rasa Shastra (Vedic
chemistry).

44.  The major therapeutic actions of Bhasma are their ability for
Immunomodulation and anti-aging property (Rasayana) and ability to
target drugs to the site.
 Ayurvedic preparations are claimed to be nontoxic, absorbed readily, and
biocompatible.
 Bhasma is an important Ayurvedic formulation comprising mixture of
herbs and metals.
 Bhasma are nearer to nanocrystallite materials which are solid composed
of crystallite with sizes less than 100 nm, at least in one dimension.
 Ayurvedic metallic nanocrystallite or Bhasma have unique
physicochemical properties such as biocompatibility and ease of surface
fictionalization.

45.  The nanotechnology in Ayurvedic drugs have application in:
1. molecular detection
2. targeted delivery
3. biological imaging.
 application of Nano-carriers for the delivery of Ayurvedic drugs can be a
great initiative because such carriers are capable to cross the plasma
membrane and deliver the drug in the desired concentration at the
specific site of action. Integration of Ayurveda and nanotechnology may
provide the best medicines to treat various life-threatening diseases.
 Nanoparticles are used in various sensors such as Gas sensors, Chemical
sensors, artificial tongue, humidity sensors etc

46. Attributes of Nanotechnology
 Nanoparticles are used in solar cell devices
 Nanoparticles are used in memory storage devices such as memristers
 Nanoparticles are in super-capacitors to store electrical energy
 Nanoparticles are in electrochromic materials
 Nanoparticles are used in the area of veterinary and human medicine.
Today we observe that efficiency of antibiotics against a pathogenic
bacterium gets decrease after frequent uses. It is difficult to have new
antibiotics. It has been observed that many nanoparticles especially silver
nanoparticles show high antimicrobial activities.

47. PART IV
Environmental Aspects Of
Nanoparticles

48. POSITIVE IMPACT OF NMs
Nanotechnology promises significant social, environmental, and financial benefits. Nanotechnology may
ultimately be developed to help decrease the human footprint on the environment by providing more
efficient and energy saving innovations.

49. NEGATIVE IMPACT OF NMs
As the environmental impacts of NMs cannot be clearly diagnosed and there are too many variables to
account for (e.g., NMs identification, low detection limits, and unknown environmental concentrations), it
is very difficult to reach any conclusion about the ecological effects and environmental stability of NMs.
Even a minor change in the chemical structure of NMs could radically change their properties, turning them
into toxic compounds. According to the United States Environmental Protection Agency, “the toxicity of
NMs is difficult to identify because they have unique chemical properties, high reactivity, and do not
dissolve in liquid”

50. Analysis of Materials at Nanoscale
 The nanomaterials are so small that they cannot be visualized by naked
eyes.
 The properties of materials at nanoscale depends upon size, shape,
morphology, interatomic distance, electrostatic forece of attraction or
repulsion, secondary bonds like van der waal’s interaction etc.
 It is possible to determine the properties of the materials at nanoscale
using advanced characterization techniques such as XRD, Scanning
Electron Microscopy, Transmission Electron Microscopy, Zeta Potential
etc.

51. Characterization Techniques
 . The instruments used for analysis are of two types i.e. 1) spectroscopes
and 2) microscopes.
 A. Spectroscopy: It is a branch of science that deals with the interaction
of electromagnetic radiations with the matter. Spectroscopy is the most
powerful tool available for the study of atomic and molecular structure
and is used in the analysis of a wide range of samples.
 B. Microscopic Techniques
 Microscopy is the technical field of using a microscope to view samples
and objects that cannot be seen with the unaided eye. There are three
well-known branches of microscopy; optical, electron, and scanning
probe microscopy.

52.  Optical and electron microscopy involve the diffraction, reflection, and
refraction of electromagnetic radiation/ electron beam interacting with
the specimen and the subsequent collection of this scattered radiation or
another signal to create an image. This process may be carried out by
wide-field irradiation of the sample (e.g. Transmission Electron
Microscope) or by scanning a fine beam over the sample (e.g. Scanning
Electron Microscope).

53. Glimpses on experimental Techniques Used For
Nanomaterial Characterization
Abbreviation Characterization
Techniques
Main Information (Utility)
XRD X-Ray Diffraction Crystal structure,
composition, crystallite size,
XAS X-Ray Absorption
Spectroscopy
X-ray absorption co-efficient,
chemical state of species,
interatomic distances, Debye-
Waller factors, and non-
crystalline NPs

54. Glimpses on experimental Techniques Used For
Nanomaterial Characterization
Abbreviation Characterization Techniques Main Information (Utility)
SAXS Small Angle X-Ray Scattering Particle size, size distribution, growth kinetics
XPS X-ray photoelectron Spectroscopy Electronic structure, elemental composition,
oxidation states, ligand binding
FT-IR Fouier Trasform Infrared Spectroscopy Surface composition, ligand binding
NMR Nuclear Magnetic Resonance
Spectroscopy
Ligand density and arrangements, electronic
core structure, atomic composition, the
influence of ligands on NP shape, NP size
BET Brunauer Emmett Teller Surface area

55. Glimpses on experimental Techniques Used For Nanomaterial
Characterization
Abbreviation Characterization Techniques Main Information (Utility)
TGA Thermogravimetric Analysis Mass and composition of stabilizers
LEIS Low Energy Ion Scattering Thickness and chemical composition of self-assembled
monolayers of NPs
UV-Visible
spectroscopy
Ultra-violet Visible Spectroscopy Optical properties, size, concentration, and
agglomeration state, hints at nanoparticles shape
PL Spectroscopy Photoluminescence spectroscopy Optical properties, relation to structural features such as
defects, size, composition, etc
DLS Dynamic Light Scattering Hydrodynamic size, detection of agglomeration
NTA Nanoparticle Tracking Analysis Nanoparticles size and their distribution
DCA Direct Coupling Analysis Nanoparticles size and their distribution
ICP-MS Inductively Coupled Plasma Mass Spectroscopy Elemental composition, size, size distribution, NP
concentration

56. Glimpses on experimental Techniques Used For Nanomaterial
Characterization
Abbreviation Characterization Techniques Main Information (Utility)
SIMS ToF-
SIMS,MALDI
Sputtering Ion Mass Spectroscopy Chemical information on functional groups especially surface
sensitivity, molecular orientation, and conformation, surface
topography, MALDI for nanoparticle size
VSM Vibrating Sample Magnetometer Magnetic properties of nanomaterials
Contact Angle Contact Angle Determination of hydrophobic characters of thin films
FMR Ferromagnetic Resonance Spectroscopy Nanoparticle size and distribution, shape, crystallographic
imperfections, surface composition, M value, magnetic anisotropic
constant, demagnetization fields
XMCD X-Ray Magnetic Circular Dichroism Site symmetry and magnetic moments of transition metal ions in
ferro and ferri magnetic materials element-specific

57. Glimpses on experimental Techniques Used
For Nanomaterial Characterization
Abbreviation Characterization Techniques Main Information (Utility)
CLSM Confocal Laser Scanning
Microscope
Imaging, ultrafine morphology
BAM Brewster Angle Microscope Gas-liquid interface imaging
APM Atomic Probe Microscopy Three Dimensional Imaging
MFM Magnetic Force Microscopy Magnetic Material Analysis
Low Energy
Electron
Diffraction
Low Energy Electron Diffraction Surface/Adsorbate bonding

58. Glimpses on experimental Techniques Used
For Nanomaterial Characterization
Abbrevi
ation
Characterization Techniques Main Information (Utility)
AEM Auger Electron Microscopy Chemical Surface Analysis
CFM Chemical Force Microscopy Chemical/Surface Analysis
FIM Field Ion Microscopy Chemical Profile/ Atomic spacing
UPS Ultraviolet Photoemission
Spectroscopy
Surface Analysis
AAS Atomic Absorption Spectroscopy Chemical Analysis

59. Glimpses on experimental Techniques Used For Nanomaterial
Characterization
Abbreviation Characterization Techniques Main Information (Utility)
ICM Inductively Coupled Microscopy Elemental Analysis
SANS Small Angle Neutran Scattering Surface Characterization
CL Cthodoluminescence Characteristic Emission
Nanocalorimetry Nanocalorimetry Latent Heat of Fusion
Sears Method Sears Method Colloidal size, specific surface area
FS Fluorescent Spectroscopy Elemental Analysis
LSPR Localized Surface Plasmon Resonance Nanosized particle Analysis
Rutherford
Backscattering
Rutherford Backscattering Quantitative Elemental Analysis
TEM Transmission Electron Microscopy NP size, size monodispersity shape, aggregation state, detect and localize quantify
nanoparticles in matrices, study growth kinetics
HRTEM High-Resolution Transmission Electron
Microscopy
All information by conventional TEM and also on the crystal structure of a single
particle. It is used to distinguish between monocrystalline, polycrystalline, and

60. Glimpses on experimental Techniques Used For Nanomaterial
Characterization
Abbreviatio
n
Characterization
Techniques
Main Information (Utility)
Liquid TEM Liquid Transmission Electron
Microscopy
Depict nanoparticle growth in real-time, study growth mechanism,
single particle motion, and superlattice formation
Cryo-TEM Cryo Transmission Electron
Microscopy
Study complex growth mechanisms, and aggregation pathways, good for
molecular biology and colloidal chemistry to avoid the presence of
artifacts or destroyed samples
ED Electron Diffraction Crystal structure, lattice parameter, study order, and disorder
transformation, long-range order parameters
STEM Scanning Transmission
Electron Microscopy
Combined with HAADF, and EDX for morphology study, crystal
structure, and elemental composition, Study the atomic structure of
hetero-interface

61. Glimpses on experimental Techniques Used For Nanomaterial
Characterization
Abbreviation Characterization Techniques Main Information (Utility)
Aberration- corrected
(STEM, TEM)
Aberration corrected Scanning Transmission
Electron Microscopy
Atomic structure of NP clusters, especially bimetallic ones, as
a function of composition, alloy, homogeneity, phase
segregation
EELS Electron Energy Loss Spectroscopy Type and quantity of atoms present, chemical states of atoms,
collective interaction of atoms with neighbors, bulk plasma
resonance
Electron tomography Electron tomography Realistic 3D particle visualization, snapshots, video, and
quantitative information down to atomic scale
SEM-HRSEM, T-SE-
EDX
Scanning Electron Microscopy- High-
Resolution Scanning Electron Microscope
Morphology, dispersion of nanoparticles in cells and other
matrices/ supports, precision in the lateral dimension of
nanoparticles, quick examination-elemental composition

62. Glimpses on experimental Techniques Used For
Nanomaterial Characterization
Abbreviation Characterization Techniques Main Information (Utility)
EBSD Electron Backscattered
Diffraction Microscopy
Structure, crystal orientation, and phase of matrices in
SEM. Examine microstructure, reveal texture, defects,
grain morphology, deformation
AFM Atomic Force Microscope Nanoparticle size and shape in 3D mode, evaluate the
degree of covering of a surface with nanoparticle
morphology, dispersion of nanoparticles in cell and
other matrices/ supports, precision in the lateral
dimension of nanoparticles, quick examination-
elemental composition

63. Nanoscale Parameters Characterization
Entity Characterized Possible Characterization Techniques
Size ( structural
properties)
TEM, XRD, DLS, NTA, SAXS, HRTEM, SEM,
AFM, EXAFM, FMR, DCS, ICP-MS, UV-Vis,
MALDI, NMR, TRPS, EPLS, magnetic
susceptibility
Shape TEM, HRTEM, AFM, EPLS, FMR, 3D-
tomography

64. Nanoscale Parameters Characterization
Techniques
Elemental chemical
composition
XRD, XPS, ICP-MS, ICP-OES, SEM-EDX, NMR, MFM, LEIS
Crystal structure XRD, EXAFS, HRTEM, STEM, electron diffraction
Size distribution DCS, DLS, SAXS, NTA, ICP-MS, FMR, DTA, TRPS, SEM,
superparamagnetic relaxometry
Magnetic properties SQUID, VSM, MFM, FMR, XMCD, magnetic susceptibility

65. Nanoscale Parameters Characterization
Techniques
Detection of Nanoparticles TEM, SEM, STEM, EBSD, magnetic susceptibility
Structural defects HRTEM, EBSD
Dispersion of nanoparticles in
matrices
SEM, AFM, TEM
3D visualization 3D topography, AFM, SEM
Single-particle properties Sp-ICP-MS, UV-Vis, RMM-MEMS,PTA,DCS,TRPS
Density DCS, RMM-MEMS

66. Nanoscale Parameters Characterization
Techniques
Agglomeration state Zeta potential, DLS, DCS, UV-Visible spectroscopy, SEM,
Cryo-TEM, TEM
Concentration ICP-MS, UV-Visible, RMM-MEMS, PTA, DCS, TRPS
Surface charges Zeta potential, EPM
Surface area, specific surface area BET, liquid NMR
Ligand binding/ composition/
density/ arrangement/ mass,
surface composition
XPS, FTIR, NMR, SIMS, FMR, TGA, SANS
Growth kinetics SAXS, NMR, TEM, cro- TEM, liquid-TEM
Chemical state –oxidation state XAS, EELS, XPS, Mossbauer

67. Thank You