Title of Invention

A PROCESS FOR PREPARATION OF MONO AND BIMETALLIC NANOPARTICLES

Abstract The present invention relates to a process for preparation of mono and bimetallic nanoparticles, comprising reacting suitable metal salts and reducing extracts from different parts of various plants at a temperature in the range 15-100°C, such that the under the reducing action of the said extract the metal ions are reduced into metal nanoparticles with different size and shape in aqueous medium.
Full Text Yet another object of this invention is to provide a generic, low-cost process for
producing mono and bimetallic nanoparticles.
Summary of the Invention
The invention relates to a process for synthesis of mono and bimetallic nanoparticles,
comprising reacting suitable metal salts and reducing extracts from different parts of
various plants at a temperature in the range 15 to 100°C, such that the under reducing
action of the said extract the metal ions are reduced into metal nanoparticles with
different size and shape in aqueous medium.
Detailed Description of the Invention
Accordingly, the present invention provides a process for preparation of mono and/or
bimetallic nanoparticles, comprising, characterized in that,
(a) reacting an aqueous metal ion solution and/or a mixture of two metal ion solutions such as herein described with an aqueous extract the concentration of the metal salts in the aqueous solution is within the range 10-6 to 10-2 M selected from the group comprising of
■ Meliaceae: Azadirachta indica
■ Poaceae: Cymbopogon Jlexuosus, Cymbopogon winterianus, Cymbopogon martinii, Oryza sativa, Triticum aestivum, Saccharum officinarum.
■ Lamiaceae : Mentha arvensis, Mentha citrata, Ocimum basilicum,
■ Apocynaceae: Catharanthus roseus, Ranvolfia serpentina
■ Myrtaceae: Eucalyptus globulus, Syzygium cumini
■ Euphorbiaceae: Phyllanthus amarus, Phyllanthus emblica
■ Pinaceae/Coniferae: Pinus roxburghii
■ Myrtaceae: Psidium guajava
■ Rosaceae: Rosa damascena
■ Santalaceae: Santalum album
■ Caesalpiniaceae: Tamarindus indica, Cassia fistula, Cassia tora
■ Fabaceae: Trigonellafoenum-graecum, Pisum sativum
■ Oleaceae: Jasminum grandiflorum
■ Labiatae: Rosmarinus officinalis, Pogostemon sp.
■ Solanaceae: Datura metel, Lycopersicon esculentum, Withania somnifera, Atropa belladonna, Duboisia sp., Hyoscyamus sp.
■ Apiaceae: Daucus carota, Coriandrum sativum, Centella asiatica, Anethum graveolens
■ Rutaceae : Citrus limon
■ Fabaceae : Cicer arietinum
■ Rubiaceae : Cinchona officinalis
■ Musaceae : Musa paradisiaca
■ Cycadaceae : Cycas circinalis
■ Zingiberaceae : Costus speciosus
■ Araceae : Colocasia esculenta
■ Vitaceae : Cissus quadrangularis
■ Moraceae : Ficus benghalensis
■ Rhamnaceae : Zizipus mauritiana
■ Liliaceae : Gloriosa superba
■ Papaveraceae : Papaver somniferum
■ Piperaceae : Piper betle
■ Brassicaceae : Raphanus sativa

■ Cannabinaceae : Cannabis sativa
■ Caricaceae : Carica papaya
■ Marsileaceae : Marsilea quadrifolia
■ Scrophulariaceae: Bacopa monnieri, Digitalis sp.
■ Papilionaceae: Glycyrrhiza glabra
■ Dioscoreaceae: Dioscorea sp.
■ Plumbaginaceae: Plantago ovata
■ Compositae: Artemisia sp.
■ Lauraceae: Cinnamomum sp.
■ Umbelliferae: Foeniculum vulgare
■ Chenopodiaceae: Spinacia oleracea
■ Compositae: Chamomilla recutita in water for a period of at least 30 minutes in a temperature range of 15 to 100°C to obtain a mono and bimetallic nanoparticle mixture,
(b) separating the nanoparticles from the mixture by conventional methods. In one of the embodiments of the present invention, the nanoparticles may be of different size and shapes such as spherical, triangular, rod shaped and/or cubic or of uniform size and shape depending on the extract of the plant used, ranging in size from 1 nanometer to 100 nanometers for spherical particles and from 1 nm to 5 microns for non-spherical particles.
In another embodiment the plants from whose extracts are obtained for the synthesis of mono and bimetallic nanoparticles are from different families exemplified herein below but not restricted to:

■ Meliaceae: Azadirachta indica
■ Geraniaceae: Pelargonium graveolens
■ Poaceae: Cymbopogon Jlexuosus, Cymbopogon winterianus, Cymbopogon martinii, Oryza sativa, Triticum aestivum, Saccharum officinarum.
■ Lamiaceae : Mentha arvensis, Mentha citrata, Ocimum basilicum,
■ Apocynaceae: Catharanthus roseus, Rauvolfla serpentina
■ Myrtaceae: Eucalyptus globulus, Syzygium cumini
■ Euphorbiaceae: Phyllanthus amarus, Phyllanthus emblica
■ Pinaceae/Coniferae: Pinus roxburghii
■ Myrtaceae: Psidium guajava
■ Rosaceae: Rosa damascena
■ Santalaceae: Santalum album
• Caesalpinlaceae: Tamarindus indica, Cassia fistula, Cassia tora
• Fabaceae: Trigonella foenum-graecum, Pisum sativum
• Oleaceae: Jasminum grandiflorum
• Labiatae: Rosmarinus officinalis, Pogostemon sp.
• Solanaceae: Datura motel, Lycopersicon esculentum, Withania somnifera,
Atropa belladonna, Duboisia sp., Hyoscyamus sp.
• Apiaceae: Daucus carota, Coriandrum sativum, Centella asiatica, Anethum
graveolens
• Rutaceae : Citrus limon
• Fabaceae : Cicer arietinum
• Rublaceae : Cinchona officinalis
• Musaceae ; Musa paradisiaca
• Cycadaceae: Cycas circinalis
• Zlngiberaceae : Costus speciosus
• Araceae : Co/ocas/a esculenta
• Vitaceae : Cissus quadrangularis
• Moraceae : Ficus benghalensis
• Rhamnaceae: Zizipus mauritiana
• Liliaceae : Gloriosa superba
• Papaveraceae : Papaver somniferum
• Plperaceae : Piper betle
• Brassicaceae : Raphanus sativa
• Cannabinaceae: Cannabis sativa
• Caricaceae : Carica papaya
• Marsileaceae: Mars/tea quadhfolia
• Scrophulariaceae: Bacopa monnieri, Digitalis sp.
• Papilionaceae: Glycyrrhiza glabra
• Dloscoreaceae: Dioscorea sp.
• Plumbaginaceae: Plantago ovata
• Cotnposltae: Artemisia sp.
• Lauraceae: Cinnamomum sp.
« Umbelliferae: Foenlculum vulgare
• Chenopodlaceae: Spinacia oleracea
• Composltae: Chamomilla recutita

In still another embodiment of the present invention, the extracts from different parts of
plant or plants are used for synthesis of mono and bimetallic nanoparticles.
In still another embodiment of the invention, the different part of the plants is selected
from the group consisting of leaf, flower, stem and root.
In still another embodiment of the present invention, the metal nanoparticles that may be
synthesized using the said process are of Au, Ag, Pt, Pd and Cu.
In still another embodiment of the present invention, the bimetallic nanoparticles that
may be synthesized by the said process are of 'composition Au/Ag, Au/Pt, Au/Pd, Au/Cu,
Ag/Pt, Ag/Pd, Ag/Cu, Pt/Pd, Pt/Cu and Pd/Cu.
In still another embodiment of the present invention, the said metal ion solution is
prepared by dissolving salts or acids of said metal ion in water.
In still another embodiment of the present invention, the said metal ion solution is
selected from the group consisting of halide, sulfate and nitrate.
In another embodiment of the present invention, the concentration of metal salts may be
varied from 10* to 10'2 M.
In still another embodiment of the present invention, the primary control .over the particle
size and shape is determined by the concentration of the metal ions and also by the
plant extract and the type of the plant extract.
In still another embodiment of the present invention, various mono and bimetallic
nanoparticles produced in accordance with one embodiment of the process of this
invention have generally uniform particle sizes and shapes ranging from 1 nm to 500
nm.
The following examples are given by way of illustration of the present invention and
should not be construed to limit the scope of the invention:
EXAMPLE 1
This example illustrates the synthesis of gold nanoparticles with leaf extract of
Pelargonium Graveolens. In a typical experiment, 20 g of thoroughly washed and finely
cut Pelargonium Graveolens leaves were boiled in a 500 ml Erlenmeyer flask with 100
ml sterile distilled water for 2 min. After boiling, the solution was decanted and filtered.
5 mL of the broth thus obtained was added to 50 ml of 2 X 10"3 M HAuCI4 aqueous
solution and kept in dark for 5 hour. After 5 hour the nanoparticles were separated out by
centrifugation and redispersed in double distilled water.
EXAMPLE 2
This example illustrates the synthesis of silver nanoparticles with leaf extract of

Pelargonium Graveolens. In a typical experiment, 20 g of thoroughly washed and finely cut Pelargonium Graveolens leaves were boiled in a 500 mL Erienmeyer flask with 100 mL sterile distilled water for 2 min. After boiling, the solution was decanted and filtered. 5 mL of the broth thus obtained was added to 2 X 10"3 M AgNO3 aqueous solution and kept in dark for 5 hour. After 5 hour the nanoparticles were separated out by centrifugation and redispersed in double distilled water. EXAMPLE 3
This example illustrates the synthesis of platinum nanoparticles with stem extract of Pelargonium Graveolens. In a typical experiment, 20 g of thoroughly washed and finely cut Pelargonium Graveolens stem pieces were boiled in a 500 mL Erienmeyer flask with 100 mL sterile distilled water for 2 min. Aftei* boiling, the solution was decanted and filtered. 5 rnL of the broth thus obtained was added to 50 mL of 2 X 1Q-3 M H2PtCI6 aqueous solution and kept in dark for 5 hour. After 5 hour the nanoparticles were separated out by centrifugation and redispersed in double distilled water. EXAMPLE 4
This example illustrates the synthesis of palladium nanoparticles with root extract of Pelargonium Graveolens. In a typical experiment, 20 g of thoroughly washed and finely cut Pelargonium Graveolens root pieces were boiled in a 500 mL Erienmeyer flask with 100 mL sterile distilled water for 2 min. After boiling, the solution, was decanted and filtered. 5 mL of the broth thus obtained was added to 50 mL of 2 X 10~3 M Pd(NO3)2 aqueous solution and kept in dark for 5 hour. After 5 hour the nanoparticles were separated out by centrifugation and redispersecj in double distilled water. EXAMPLE 5
This example illustrates the synthesis of gold nanoparticles with leaf extract of Cymbopogon flexuosus. In a typical experiment, 20 g of thoroughly washed and finely cut Cymbopogon flexuosus leaves were boiled in a 500 mL Erienmeyer flask with 100 mL sterile distilled water for 2 min. After boiling, the solution was decanted and filtered. 5 mL of the broth thus obtained was added to 50 mL of 2 X 10"3 M HAuCI4 aqueous solution and kept in dark for 5 hour. After 5 hour the nanoparticles were separated out by centrifugation and redispersed in double distilled water. EXAMPLE 6
This example illustrates the synthesis of gold-silver bimetallic nanoparticles with leaf extract of Azadirachta indica. In a typical experiment, 20 g of thoroughly washed and finely cut Azadirachta Indica leaves were boiled in a 500 mL Erienmeyer flask with 100 mL sterile distilled water for 2 min. After boiling, the solution was decanted and filtered.
10 ml of the broth thus obtained was added to 50 mL of 2 X tO"3 M HAuCJ4 and 50 mL
of 2 X 10"3 M AgN03 aqueous solution and kept in dark for 5 hour. After 5 hour the
ranoparticles were separated out by centrifugatio.n and redispersed in double distilled
water.
Advantages of trie process claimed In the present Invention are:
1. Large scale synthesis is possible
2. Require less maneuvering.
3. Ambient experimental conditions.
4. Fast biological process.
5. Nanoparticles are synthesized extracellularly.
6. Isolation of the extraceilulariy synthesized nanoparticles is simple.
7. Cost effective/Economical system for the industry
8. Highly stable colloidal mono and bimetallic nanoparticles can be formed,
9. Nanoparticles of different shapes can be formed.
9. Environment friendly process.
10. Plant used for synthesis of nanoparticles can be easily grown anywhere.
11. Preparation of plant extract is very simple
12. Possibility of the reusability of nanoparticles.









We Claim:
1. A process for preparation of mono and/or bimetallic nanoparticles, comprising, characterized in that
(a) reacting an aqueous metal ion solution and/or a mixture of two metal ion solutions such as herein described with an aqueous extract the concentration of the metal salts in the aqueous solution is within the range 10-6 to 10-2 M selected from the group comprising of
■ Meliaceae: Azadirachta indica
■ Poaceae: Cymbopogon flexuosus, Cymbopogon winterianus, Cymbopogon martinii, Oryza sativa, Triticum aestivum, Saccharum offlcinarum.
■ Lamiaceae : Mentha arvensis, Mentha citrata, Ocimum basilicum,
■ Apocynaceae: Catharanthus roseus, Rauvolfia serpentina
■ Myrtaceae: Eucalyptus globulus, Syzygium cumini
■ Euphorbiaceae: Phyllanthus amarus, Phyllanthus emblica
■ Pinaceae/Coniferae: Pinus roxburghii
■ Myrtaceae: Psidium guajava
■ Rosaceae: Rosa damascena
■ Santalaceae: Santalum album
■ Caesalpiniaceae: Tamarindus indica, Cassia fistula, Cassia tora
■ Fabaceae: Trigonella foenum-graecum, Pisum sativum
■ Oleaceae: Jasminum grandiflorum
■ Labiatae: Rosmarinus officinalis, Pogostemon sp.
■ Solanaceae : Datura metel, Lycopersicon esculentum, Withania somnifera, Atropa belladonna, Duboisia sp., Hyoscyamus sp.
■ Apiaceae: Daucus carota, Coriandrum sativum, Centella asiatica, Anethum graveolens
■ Rutaceae : Citrus limon
■ Fabaceae : Cicer arietinum
■ Rubiaceae : Cinchona officinalis
■ Musaceae : Musa paradisiaca
■ Cycadaceae : Cycas circinalis
■ Zingiberaceae : Costus speciosus
■ Araceae : Colocasia esculenta
■ Vitaceae : Cissus quadrangularis
■ Moraceae : Ficus benghalensis
■ Rhamnaceae : Zizipus mauritiana
■ Liliaceae : Gloriosa superba
■ Papaveraceae : Papaver somniferum
■ Piperaceae : Piper betle
■ Brassicaceae : Raphanus sativa
■ Cannabinaceae : Cannabis sativa
■ Caricaceae : Carica papaya
■ Marsileaceae : Marsilea quadrifolia
■ Scrophulariaceae: Bacopa monnieri, Digitalis sp.
■ Papilionaceae: Glycyrrhiza glabra
■ Dioscoreaceae: Dioscorea sp.
■ Plumbaginaceae: Plantago ovata
■ Compositae: Artemisia sp.
■ Lauraceae: Cinnamomum sp.
■ Umbelliferae: Foeniculum vulgare
■ Chenopodiaceae: Spinacia oleracea
■ Compositae: Chamomilla recutita in water for a period of at least 30 minutes in a temperature range of 15 to 100°C to obtain a mono and bimetallic nanoparticle mixture,
(b) separating the nanoparticles from the mixture by conventional methods.
2. A process as claimed in claim 1,wherein said metal ions for synthesis of said mono metal nanoparticles are selected from the group consisting of Au, Ag, Pt, Pd and Cu.
3. A process as claimed in claim 1,wherein said metal ions for synthesis of said bimetallic nanoparticles are combination of two metal ions selected from the group consisting of Au, Ag, Pt, Pd and Cu.

4. A process as claimed in claim 1,wherein said metal ion solution used for the preparation of the said metal ion solution is selected from the group consisting of halide, sulfate and nitrate.


Documents:

2996-DELNP-2006-Abstract-(17-08-2009).pdf

2996-delnp-2006-abstract.pdf

2996-DELNP-2006-Claims-(17-08-2009).pdf

2996-DELNP-2006-Claims-(24-11-2009).pdf

2996-delnp-2006-claims.pdf

2996-delnp-2006-correpondence-1.pdf

2996-DELNP-2006-Correspondence-Others-(17-08-2009).pdf

2996-DELNP-2006-Correspondence-Others-(24-11-2009).pdf

2996-delnp-2006-correspondence-others.pdf

2996-DELNP-2006-Description (Complete)-(17-08-2009).pdf

2996-DELNP-2006-Description (Complete)-(24-11-2009).pdf

2996-delnp-2006-description (complete).pdf

2996-DELNP-2006-Form-1-(17-08-2009).pdf

2996-delnp-2006-form-1.pdf

2996-delnp-2006-form-18.pdf

2996-DELNP-2006-Form-2-(17-08-2009).pdf

2996-delnp-2006-form-2.pdf

2996-DELNP-2006-Form-3-(17-08-2009).pdf

2996-delnp-2006-form-3.pdf

2996-delnp-2006-form-5.pdf

2996-delnp-2006-pct-210.pdf


Patent Number 237381
Indian Patent Application Number 2996/DELNP/2006
PG Journal Number 52/2009
Publication Date 25-Dec-2009
Grant Date 17-Dec-2009
Date of Filing 24-May-2006
Name of Patentee COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH,
Applicant Address ANUSANDHAN BHAWAN, RAFI MARG, NEW DELHI 110 001, INDIA.
Inventors:
# Inventor's Name Inventor's Address
1 SASTRY MURALI NATIONAL CHEMICAL LABORATORY DR. HOMI BHABHA ROAD PUNE - 411008, MAHARASHTRA, INDIA.
2 AHMAD ABSAR NATIONAL CHEMICAL LABORATORY DR. HOMI BHABHA ROAD PUNE - 411008, MAHARASHTRA, INDIA.
3 SANGARU SHIV SHANKAR NATIONAL CHEMICAL LABORATORY DR. HOMI BHABHA ROAD PUNE - 411008, MAHARASHTRA, INDIA.
PCT International Classification Number C08
PCT International Application Number PCT/IN04/00082
PCT International Filing date 2004-03-31
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA