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Nanoparticles
Nanoparticles
Pakistan.
Table of Contents:
Introduction ................ 03 Background 04 Physical properties ............................................. 05 Sizing nanoparticles .. 10 Characterization 11 Synthesis of nanoparticles 11 Advantages of synthesis 19 Synthesis of Iron oxide nanoparticles 20 Synthesis of Silver nanoparticles . 21 Applications of nanoparticles .. 22 Applications of nanoparticles in Consumer goods . 26 Human and environmental health and safety 27 Innovative aspects of this project 28 Current state of the development in Pakistan . 29 Collaboration sought ... 30 References 31
Nanoparticles
Introduction:
"A particle having one or more dimensions of the order of 100nm or less". In nanotechnology, a particle is defined as a small object that behaves as a whole unit in terms of its transport and properties. Particles are further classified according to size: in terms of diameter, fine particles cover a range between 100 and 2500 nanometers. On the other hand, ultrafine particles are sized between 1 and 100 nanometers. Similar to ultrafine particles, nanoparticles are sized between 1 and 100 nanometers. Nanoparticles may or may not exhibit size-related properties that differ significantly from those observed in fine particles or bulk materials. Although the size of most molecules would fit into the above outline, individual molecules are usually not referred to as nanoparticles. Nanoclusters have at least one dimension between 1 and 10 nanometers and a narrow size distribution. Nanopowders are agglomerates of ultrafine particles, nanoparticles, or nanoclusters. Nanometer-sized single crystals, or single-domain ultrafine particles, are often referred to as nanocrystals. Nanoparticle research is currently an area of intense scientific interest due to a wide variety of potential applications in biomedical, optical and electronic fields.
Transmission Electron Microscopy (a, b, and c) images of prepared mesoporous silica nanoparticles with mean outer diameter: (a) 20nm, (b) 45nm, and (c) 80nm. Scanning Electron Microscopy (d) image corresponding to (b). The insets are a high magnification of mesoporous silica particle.
Background:
Although nanoparticles are generally considered an invention of modern science, they actually have a very long history. Nanoparticles were used by artisans as far back as the 9th century in Mesopotamia for generating a glittering effect on the surface of pots. Even these days, pottery from the Middle Ages and Renaissance often retain a distinct gold or copper colored metallic glitter. This so called luster is caused by a metallic film that was applied to the transparent surface of a glazing. The luster can still be visible if the film has resisted atmospheric oxidation and other weathering. Michael Faraday provided the first description, in scientific terms, of the optical properties of nanometer-scale metals in his classic 1857 paper. In a subsequent paper, the author (Turner) points out that: "It is well known that when thin leaves of gold or silver are mounted upon glass and heated to a temperature which is well below a red heat (~500 C), a remarkable change of properties takes place, whereby the continuity of the metallic film is destroyed. The result is that white light is now freely transmitted, reflection is correspondingly diminished, while the electrical resistivity is enormously increased."
Review of literature:
The first mention of some of the distinguishing concepts in nanotechnology (but predating use of that name) was in 1867 by James Clerk Maxwell when he proposed as a thought experiment a tiny entity known as Maxwell's Demon able to handle individual molecules. The first observations and size measurements of nano-particles was made during the first decade of the 20th century. They are mostly associated with Richard Adolf Zsigmondy who made a detailed study of gold sols and other nanomaterials with sizes down to 10 nm and less. He published a book in 1914. He used ultramicroscope that employes the dark field method for seeing particles with sizes much less than light wavelength. Zsigmondy was also the first who used nanometer explicitly for characterizing particle size. He determined it as 1/1,000,000 of millimeter. He developed the first system classification based on particle size in the nanometer range. There have been many significant developments during the 20th century in characterizing nanomaterials and related phenomena, belonging to the field of interface and colloid science. In the 1920s, Irving Langmuir and Katharine B. Blodgett introduced the concept of a monolayer, a layer of material one molecule thick. Langmuir won a Nobel Prize in chemistry for his work. In the early 1950s, Derjaguin and Abrikosova conducted the first measurement of surface forces. 4
Physical properties:
Nanoparticles are of great scientific interest as they are effectively a bridge between bulk materials and atomic or molecular structures. A bulk material should have constant physical properties regardless of its size, but at the nano-scale size-dependent properties are often observed.
1. Surface area:
Thus, the properties of materials change as their size approaches the nanoscale and as the percentage of atoms at the surface of a material becomes significant. For bulk materials larger than one micrometer (or micron), the percentage of atoms at the surface is insignificant in relation to the number of atoms in the bulk of the material. The interesting and sometimes unexpected properties of nanoparticles are therefore largely due to the large surface area of the material, which dominates the contributions made by the small bulk of the material.
Silicon nanopowder
2. Optical properties:
Nanoparticles often possess unexpected optical properties as they are small enough to confine their electrons and produce quantum effects. For example gold nanoparticles appear deep red to black in solution. Nanoparticles of usually yellow gold and gray silicon are red in color. Gold nanoparticles melt at much lower temperatures (~300 C for 2.5 nm size) than the gold slabs (1064 C); And absorption of solar radiation in photovoltaic cells is much higher in materials composed of nanoparticles than it is in thin films of continuous sheets of material. I.E. the smaller the particles, the greater the solar absorption.
Gold nanoparticles
3. Uniformity:
It is desirable to process a material in such a way that it is physically uniform with regard to the distribution of components and porosity, rather than using particle size distributions which will maximize the green density. The containment of a uniformly dispersed assembly of strongly interacting particles in suspension requires total control over interparticle forces. Monodisperse nanoparticles and colloids provide this potential. Monodisperse powders of colloidal silica, for example, may therefore be stabilized sufficiently to ensure a high degree of order in the colloidal crystal or polycrystalline colloidal solid which results from aggregation.
4. Functionalization:
The surface coating of nanoparticles is crucial to determining their properties. In particular, the surface coating can regulate stability, solubility and targeting. Nanoparticles can be linked to biological molecules which can act as address tags, to direct the nanoparticles to specific sites within the body, specific organelles within the cell, or to follow specifically the movement of individual protein or RNA molecules in living cells. Common address tags are monoclonal antibodies, aptamers, streptavidin or peptides.
Functionalized nanoparticle
5. Quantum confinement:
Other size-dependent property changes include quantum confinement in semiconductor particles. Metal, dielectric, and semiconductor nanoparticles have been formed, as well as hybrid structures (e.g., core-shell nanoparticles). Nanoparticles made of semiconducting material may also be labeled quantum dots if they are small enough (typically sub 10 nm) that quantization of electronic energy levels occurs. Such nanoscale particles are used in biomedical applications as drug carriers or imaging agents.
On quantum confinement
7. Suspension:
Suspensions of nanoparticles are possible since the interaction of the particle surface with the solvent is strong enough to overcome density differences, which otherwise usually result in a material either sinking or floating in a liquid.
8. Polymers (plastics):
Clay nanoparticles when incorporated into polymer matrices increase reinforcement, leading to stronger plastics, verifiable by a higher glass transition temperature and other mechanical property tests. These nanoparticles are hard, and impart 8
their properties to the polymer (plastic). Nanoparticles have also been attached to textile fibers in order to create smart and functional clothing.
9. Liposome:
Semi-solid and soft nanoparticles have been manufactured. A prototype nanoparticle of semi-solid nature is the liposome. Various types of liposome nanoparticles are currently used clinically as delivery systems for anticancer drugs and vaccines.
Sizing nanoparticles:
Perhaps the most important task at hand when making and characterizing nanoscale materials is to control the size of the particle. To an equal extent we also want to control the shape of the resulting material. Both are important parameters because as described earlier, nanoscale metals and semiconductors exhibit size and shape dependent optical, electrical and even chemical properties. The next most important task after making nanoscale materials is to determine their size. In this respect, a number of ways exist for sizing nanoscale materials. In the present laboratory we will use one of the techniques described below (dynamic light scattering) to verify the size and size distribution of chemically synthesized Au NPs. We will also provide images from another technique so that we can actually see what the particles look like. Furthermore, we will use these images as an independent way to size the particles and will verify that the two techniques provide similar values of the NP diameter.
Au NP TEM
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Characterization:
Nanoparticle characterization is necessary to establish understanding and control of nanoparticle synthesis and applications. Characterization is done by using a variety of different techniques, mainly drawn from materials science. Common techniques are electron microscopy (TEM, SEM), atomic force microscopy (AFM), dynamic light scattering (DLS), x-ray photoelectron spectroscopy (XPS), powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF), ultraviolet-visible spectroscopy, dual polarisation interferometry and nuclear magnetic resonance (NMR). Whilst the theory has been known for over a century (see Robert Brown), the technology for Nanoparticle tracking analysis (NTA) allows direct tracking of the Brownian motion and this method therefore allows the sizing of individual nanoparticles in solution.
Synthesis of nanoparticles:
The synthesis and application of nanoparticles is one of the most interesting fields of research from a basic and applied point of views. The method employed by our group is a micellar method that could be easily scaled-up and allows the control of the composition and size of the nanoparticle. Many of these nanomaterials are made directly as dry powders, and it is a common myth that these powders will stay in the same state when stored. In fact, they will rapidly aggregate through a solid bridging mechanism in as little as a few seconds.
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Whether these aggregates are detrimental will depend entirely on the application of the nanomaterial. If the nanoparticles need to be kept separate, then they must be prepared and stored in a liquid medium designed to facilitate sufficient interparticle repulsion forces to prevent aggregation. Different process of synthesis of nanoparticles are as follow:
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The molecule does not dissolve well in either aqueous or organic solvents. In an organic solvent containing a small amount of water the hexadecyltrimethylammonium bromide traps the aqueous portion in a micelle sphere with the polar heads facing in and the non-polar tails facing out. The relative amount of pentanol cosurfactant controls the size of the micelle. Mixing hexadecyltrimethylammonium bromide pentanol micelles of CdCl 2 with similar micelles containing Na2S produces nanoparticle CdS since the aqueous solution serves as a nanoreactor and the particles cannot grow bigger than the micelle. The pentanol also acts as a capping agent to stabilize the CdS particles. The formation of CdS nanoparticles can be detected by spectroscopy since quantum size effects make the visible absorption spectra different than that of bulk CdS.
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Procedure:
Test the reagents by adding a drop of aqueous Cd +2 to a drop ofaqueous S-2. A yellow color should appear if the Na2S solution is good. If the mixture remains clear, remake the Na2S solution.
In a cuvet, add an equal amount of aqueous 0.012 M Cd+2 and aqueous 0.012 M S2 . Record your observations and immediately obtain the visible absorption spectrum.
Add 0.20 g hexadecyltrimethylammonium bromide to a test tube. Add a stir bar. Clamp over a magnetic stirrer.
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Add 4.0 mL heptane and 1.0 mL pentanol to the hexadecyltrimethylammonium bromide. Stir to give a suspension.Transfer half the suspension to a second tube. Stir both solutions to maintain the suspension.
To one test tube, add 0.1 mL (3 drops) of 0.012 M CdCl 2. The solution will clear as hexadecyltrimethylammonium bromide micelles containing CdCl2 form. To the second test tube, add 0.1 mL (3 drops) of 0.012 M Na2S. The solution will clear as hexadecyltrimethylammonium bromide micelles containing Na2S form. Join the two solutions and record the absorption spectrum of the solution.
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In a similar way, Au nanoparticles can be also prepared. This method can be applied to other noble metals and their alloys. Colloidal Au nanoparticles
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3. Synthesis of nanorods:
Colloidal systems can be also applied for the synthesis of Au nanorods. The synthesis is achieved using a seeding growth method. With this synthesis length of nanorods can be controlled from 20 nm to 1 micrometre aproximately. Optical properties of this nanorods are related to the size of the particles and different colours can be obtained, red, purple, black, etc. Thus, controlling length of nanorods different colours can be prepared. Moreover, Au nanorods can also be applied in electrocatalysis.
Silicon nanorod
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Au nanorod Various gold nanoparticle shapes such as spheres, rods, wires, and cubes have been prepared and characterized using standard processing techniques by researchers. By varying the shape of the materials, their vibrant optical properties can be suitably tuned from the visible to the IR region of the spectrum. Also enhanced plasmonic properties make Au nanorods of interest for a variety of sensing and biological applications.
. Au nanorods
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Layer-by-layer assembly:
The layer-by-layer (LBL) assembly method, combined with the seeded growth technique, has been used to deposit gold shells on the surface of hematite (-Fe2O3) spindles. The LBL method yields dense coatings of preformed Au nanoparticles, while AuCl4 ions are further reduced by a mild reducing agent, thicker, rough nanostructured shells can be grown.
Green synthesis:
Gold nanorods can be prepared by electrochemically reducing gold salts in a concentrated surfactant solution.The procedure uses Silver nitrate, Ascorbic acid, Sodium borohydride, seed solution, gold solution, & CTAB and Au nanorods with a unidirectional pin-like morphology have been prepared on the surface of glassy carbon electrodes via a potential-step electro deposition method from H2SO4 solution containing Na[AuCl4].
Researchers have discovered a new method to create branched nanorods, such as those in this scanning electron microscope image. Such nanorods could one day enable new nanoscale thermoelectric devices for power generation, as well as nanoscale heat pumps for cooling hot spots in nanoelectronics devices.
Advantages of synthesis:
Customization of the process of synthesis, test, scale-up and technology transfer to the company. Use of decontaminated protocols for the cleaning of some particles. Techniques appropriated for metallic, bimetallic and multimetallic particles. Also applyable to other compounds as SiO2, CdS, ZnS, ZrO2, CaCO3, BaCO3, CdSe, TiO2, etc. 19
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Optimum conditions for this reaction are pH between 8 and 14, Fe+3/Fe+2 ratio of 2:1 and a non-oxidizing environment. Being highly susceptibile to oxidation, magnetite (Fe3O4) is transformed to maghemite (Fe2O3) in the presence of oxygen: Fe3O4 + 2H Fe2O3 + Fe2 + H2O The size and shape of the nanoparticles can be controlled by adjusting pH, ionic strength, temperature, nature of the salts (perchlorates, chlorides, sulfates, and nitrates), or the Fe(II)/Fe(III) concentration ratio.
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Also, it is important to note, not all nanoparticles are created equal. The size and shape have been shown to have an impact on its efficacy. Additionally, crystal facet size, oxide content and several other factors could also affect the antimicrobial properties.
TEM image of a two-dimensional silver nanoparticle superlattice and (inset) the histogram of the nanoparticles.
Applications of nanoparticles:
Market applications:
Optical, magnetic, catalytic and electrocatalytic properties. Sensors. Catalysts (supported and unsupported) for batteries, fuel cells, gas diffusion electrodes, etc.
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Ceramic materials. Pigments. Textile engineering. Water treatment. Silver-based consumer products e.g, Cathode in a silver-oxide battery.
Laser applications:
The use of nanoparticle distributions in laser dye-doped poly(methyl methacrylate) (PMMA) laser gain media was demonstrated in 2003 and it has been shown to improve conversion efficiencies and to decrease laser beam divergence. Researchers attribute the reduction in beam divergence to improved dn/dT characteristics of the organic-inorganic dye-doped nanocomposite. The optimum composition reported by these researchers is 30% w/w of SiO2 (~ 12 nm) in dye-doped PMMA.
Bone cement Surgical instruments Surgical masks Wound dressings Polymeric nanoparticle Liposome
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sensors can monitor temperature, humidity, and airborne toxins which needs nanotech based improved batteries. The building components will be intelligent and interactive since the sensor uses wireless components,it can collect the wide range of data.
Nanoparticles in glass:
There is a lot of research being carried out on the application of nanotechnology to glass. Titanium dioxide (TiO2) nanoparticles are used to coat glazing since it has sterilizing and anti-fouling properties. The particles catalyze powerful reactions which breakdown organic pollutants, volatile organic compounds and bacterial membranes. The TiO2 is hydrophilic (attraction to water) which can attract rain drops which then wash off the dirt particles. Thus the introduction of nanotechnology in the Glass industry, incorporates the self cleaning property of glass. Fire-protective glass is another application of nanotechnology. This is achieved by using a clear intumescent layer sandwiched between glass panels (an interlayer) formed of silica nanoparticles (SiO2) which turns into a rigid and opaque fire shield when heated.
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1. Foods:
Complex set of engineering and scientific challenges in the food and bioprocessing industry for manufacturing high quality and safe food through efficient and sustainable means can be solved through use of nanoparticles. Bacteria identification and food quality monitoring using biosensors; intelligent, active, and smart food packaging systems; nanoencapsulation of bioactive food compounds are few examples of emerging applications. This technology can be applied in the production, processing, safety and packaging of food. A nanocomposite coating process could improve food packaging by placing anti-microbial agents directly on the surface of the coated film.
2. Household:
The most prominent application of nanoparticle in the household is self-cleaning or easy-to-clean surfaces on ceramics or glasses. Nanoceramic particles have improved the smoothness and heat resistance of common household equipment such as the flat iron.
3. Optics:
The first sunglasses using protective and anti-reflective ultrathin polymer coatings are on the market. For optics, scratch resistant surface coatings based on nanocomposites are available. Nano-optics could allow for an increase in precision of pupil repair and other types of laser eye surgery.
4. Textiles:
The use of engineered nanofibers already makes clothes water- and stainrepellent or wrinkle-free. Textiles with a nanotechnological finish can be washed less frequently and at lower temperatures. It has been used to integrate tiny carbon particles membrane and guarantee full-surface protection from electrostatic charges for the wearer.
5. Cosmetics:
One field of application is in sunscreens. The traditional chemical UV protection approach suffers from its poor long-term stability. A sunscreen based on mineral nanoparticles such as titanium dioxide offer several advantages. Titanium oxide
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nanoparticles have a comparable UV protection property as the bulk material, but lose the cosmetically undesirable whitening as the particle size is decreased.
6. Agriculture:
Applications of nanoparticles have the potential to change the entire agriculture sector and food industry chain from production to conservation, processing, packaging, transportation, and even waste treatment. NanoScience concepts and Nanotechnology applications have the potential to redesign the production cycle, restructure the processing and conservation processes and redefine the food habits of the people. Major Challenges related to agriculture like Low productivity in cultivable areas, large uncultivable areas, Shrinkage of cultivable lands, Wastage of inputs like water, fertilizers, pesticides, Wastage of products and of course Food security for growing numbers can be addressed through various applications of nanoparticles in agriculture.
This project will facilitate us in all fields of life: Medicine: Researchers are developing customized nanoparticles the size of molecules that can deliver drugs directly to diseased cells in your body. When it's perfected, this method should greatly reduce the damage treatment such as chemotherapy does to a patient's healthy cells. Electronics: Nanotechnology holds answers for how we might increase the capabilities of electronics devices while we reduce their weight and power consumption. Space: It is helping in making space travelling more practical. Food: It has application in growing and packaging food. Fuel Cells: Nanotechnology is being used to reduce the cost of catalysts used in fuel cells to produce hydrogen ions from fuel such as methanol and to improve the efficiency of membrane used in fuel cells to separate hydrogen ions from other gasses such as oxygen. Solar Cells: Nanotechnology is helping to produce solar cells at low cost then other solar cells in use. Batteries: Nanotechnology is helping to produce batteries that will have more shelf life and they will be charged easily and quickly. Fuel: It will help to produce fuel from cheap raw material. 28
Batter Air Quality: Specially designed nano particles will help in produce gasses from industrial and vehicles vapors. Water cleaning: Nanotechnology has enormous application in cleaning industrial waste water. Sensors: Nanotechnology has application to develop sensors that have application in many industries. Fabric: Nanotechnology have application in composite fabric industry.
In Addition to this, Nanotechnology may also have many other potential applications in various industries and their applications will increase with time.
ISLAMABAD: Government is concentrating on establishing the Nano-technology laboratories with priority in Nano-biotechnology and establishing the synthesis and characterization techniques on the Nano-scale. Nano Science and Technology is newly growing and fast emerging field with unlimited industrial opportunities and helping to solve many problems of human welfare, may it be consumer goods or health care. All countries the world over, particularly the industrially advanced countries, are trying to reap benefits from Nanotechnology. Several developing countries are also actively and keenly pursuing to establish laboratories in this field. Talking to newsmen scientist and President National Academy of Young Scientists (NAYS) Dr Aftab Ahmed said nanotechnology is covering industries of all kinds such as Biotechnology products, auto industry, pharmaceuticals & drugs, Agriculture and Energy Sector. Realizing the importance of nano technology, he said, Pakistan has embarked on a programme of encouraging university laboratories and other research centres to work in the area of nano-technology relevant to their expertise. Aftab Ahmed said some laboratories have already hands on experience of research in nano-composites, nanomagnetics, nano-polymers and the techniques involved in the synthesis and characerisation of nano-materials thus produced. To give a more serious attention to the establishment of work on nano science and technology, Government has established recently a National Commission on NanoScience and Technology (NCNST) whose mandate is to help all universities and research centres in the country in the establishment of such laboratories. Its mandate is also to monitor the quality of research and the work done in such laboratories, he mentioned. He said some technologies are used only in specific applications, nanotechnology is not limited to certain fields and it is possible to be used in all aspects of sciences. In medicine, nanotechnology facilitates new ways of treatment through new 29
drug delivery systems. In medical imaging, nanotechnology based devices take more accurate images from cancerous tumors which might lead to a dramatic change in the treatment of cancer, he added. He elaborated one of the most important applications of nanotechnology is the environment where nanoparticles significantly increase the efficiency of groundwater pollutants filtration. Dr Aftab Ahmed said in the automotive sector, there is a growing demand for nanoscale technologies because of its high performance and efficiency, and in safety and emissions standards. Nanotechnology is currently providing solutions to unwanted heat transfer from the engine and fuel assembly components of vehicles; it would help to cool the interior parts of vehicles, allowing less work to be done by a cooling systems which is result consumes less fuel. He further said that applications of nanotechnology have the potential to change the entire agriculture sector and food industry chain from production to storage, processing, packaging, transportation, and even waste treatment. Nanotechnology has the potential to redesign the production cycle, including the restructuring process and conservation processes which redefine the food habits of people, he stated. In near future, nano structured catalysts will be available which will increase the efficiency of pesticides and herbicides, allowing lower doses to be used. President NAYS said Pakistan stands out well in setting up a nanotechnology center with the cooperation of Pakistan Council of Scientific and Industrial Research (PCSIR), where facilities are for industry to use as well as for conducting R&D that meets industry needs. Its nanotechnology lab facilities are utilized for the development, synthesis and characterization of 12 different nanocomposite coatings used in industries including Orthopedic implants & Surgical, Cutting Tool, Tool & Die and Textiles.This center focuses on nanocoating, nanomaterials and nanopowder and industry development.
Collaboration sought:
Manufacturers of optical, magnetic, sensors, medical devices, catalysts (for using in batteries, fuel cells, gas diffusion electrodes, etc.), ceramic materials and/or pigments are sought in order to achieve technical cooperation and/or commercial with technical assistance agreements. In case of technical cooperation: adapting or developing the technology for the sector or market in which the company could be involved and under their requirements. In case of commercial agreement with technical assistance: training/assisting in set up processes, consulting in new processes, technical training.
References:
www.google.com www.wikipedia.com 30
www.ask.com www.askIItians.com www.sciencedirect.com www.nanotech-now.com www.google.com/images/nanoparticles www.google.com/books/nanoparticles www.wikipedia.org/wiki/list_of_nanotechnoligy_applications www.wikipedia.org/wiki/construction www.wikipedia.org/wiki/nanoparticles www.wikipedia.org/wiki/national_nanotechnology_initiatives www.wikipedia.org/wiki/nanoparticles#background www.wikipedia.org/wiki/nanoparticles#safety www.wikipedia.org/wiki/nanoparticles#functionaization www.wikipedia.org/wiki/nanoparticles#laser_applications www.wikipedia.org/wiki/silver_nanoparticles#mw-head www.malvern.com/labeng/industry/nanotechnology/nanoparticle_research.htm www.malvern.com/LabEng/industry/nanotechnology/nanotechnology_definition.h tm www.malvern.com/labeng/industry/nanotechnology/nanoparticle_manufacturing. htm
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