Investigation of the Recent Developments in Nanoscience and their applications in the chemical industry.

Silky Ng

Abstract This essay focuses on the relatively new science of nanotechnology and the recent developments and their applications in the chemical industry. It is written for a general audience with some background knowledge in the field of physics.

Nanotechnology

Nanotechnology is the study and manipulation of structures that are between 1 - 100 nanometers in size. It is the research and development of nano-structures that exhibit certain properties and functions of use in industry because of their structure. Nanotechnology is an exciting and flourishing branch of science that is continuously developing to meet the demands of our technology driven civilisation. The world is constantly building products using technologies that have evolved from ancient traditions aeons ago, from chopping wood to making fire. Looking back in history, it is astonishing how much progression that technology has made in the last hundred years, and it seems it can only accelerate forward into the future. In the field of information technology, which has seen the birth of the electronic age in the last half century, the advancement of nanotechnology is a must to improve the computing power and efficiency of machines. As Dr. W. Adams put it, Making small stuff do big things... and then selling them! 1. In a famous lecture [1] that Richard Feynman, a nobel-prize winning physicist, gave a talk titled, Theres Plenty of Room at the Bottom, suggested that in the future it will be possible to manipulate atoms and molecules to create nano-machines. Although he did not coin the term nanotechnology, he had a vision that it would be possible to construct molecular machines on the nanoscale that are able to perform tasks with endless possibilities. There are essentially two ways to look at the development of nanoscience, one is the top-down approach which is the progressive diminutive manufacturing of components decreasing in size, which is favoured by physicists and engineers. The other is the bottom-up approach, which Feynman refers to in his lecture, starting at the opposite end from nano or even subnano scale objects to develop the bigger nanostructures. Eric Drexler, a promoter and often-renowned godfather of molecular nanotechnology had put it into context that these molecular machines or nanorobots which were called assemblers, could in fact build atoms and even replicate itself. In his book [2] Engines of Creation, he gives a wonderful insight into the possibilities of such technology and why a large investment into nanoscience is needed to innovate molecular devices. This vision of nanorobots, which was in favour of physicists, did not appeal to chemists, as they believed that physical laws to perform such tasks would restrict such a universal assembler.
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In a TED lecture on Nanotechnology and Energy, 2011

Nanotechnology is of a huge interest to chemists because nano particles have a better surface area to volume ratio and so are more reactive than most molecules. This would give the particles new properties unseen before and have the potential for chemists to create new products for use in industry and also in the pharmaceutical industry, which is often related to medicine. The research into this area developed in the 1970s when molecules could be manipulated to construct nano devices, with the insight that molecules and not atoms could be used in more variety. Also a lot chemistry is involved with the reactions of molecules and they can also be bonded to make larger structures. This led to the development of supramolecular chemistry, which came from the hypothesis of the bottom-up approach leading to the development of artificial molecular devices and machines. Within this hidden world of nanotechnology, there is potential to demonstrate man-made chemistry not found in nature and to use it for biological and chemical purposes. The molecules that are manipulated in supramolecular chemistry are rather like organs in a body designed to do specific jobs. These molecules can be assembled together like an organ system, with each part operating to perform its function. Now these devices need to have energy to operate and so they need electronic arrangements to help them communicate and carry out tasks. The energy could be given in different forms such as the absorption of photons, absorption or emission of electrons and even using a chemical reagent. The laws of physics at the nanoscale level certainly work differently compared to the macroscopic scale because quantum effects need to be considered. The factors that affect this scale include the Brownian motion affecting molecules as they are in random motion due to thermal effects. Electromagnetic interactions and the size of the molecules compared to the wavelengths of light affect the information and energy given to the devices. Because of the scale of the molecules, they would function by chemical reactions that would involve electrons and nuclear arrangements, with electrons transferring the electrical energy. There are many different functions that molecular devices and machines can perform [3], they can be used to transfer signals in the form of photons, electrons and protons, which is useful in information processing. Also they can convert light into a chemical fuel via an electrochemical potential. The recent developments in the last decade have shown that artificial molecular machines of molecular components of rotaxanes, catenanes are of high interest to chemists. Rotaxanes and Catenanes are mechanically interlocked molecules that are not connected by covalent bonds. Their components are linked to each other mechanically. The names of these are so-called because rota and axis are Latin for wheel and axle and catena for chain. The Rotaxane 2 in Figure 1 can be summarised as a dumb-bell shaped molecule with a ring in the centre. It has stoppers which stops the parts from separating. The Catenane in its simplest form consists of two interlocked rings, which are known as macrocycles. These species of interlocked molecules can be made by a method called templated synthesis. They are useful in industry because of the mechanical bonding, which allows stability and offers different arrangements of molecular components. Rotaxanes and Catenanes are made by templated synthesis, which involved undergoing a series of reactions such as metal ligand bonding, and pion-pion charge transfers which are various techniques used in synthetic chemistry3. The interesting properties that these molecular species exhibit are the movement and rotation of the ring around the axle, which allows chemists to construct linear and rotary molecular motors. Using these species, chemists have been able to create chemically controllable molecular shuttles
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Image Credit: http://rodgers.org.uk/oldsite/research/ Further information can be found: Schalley, C. A., et al., Top. Curr. Chem. (2004) 248, 141.

and elevators, and even creating molecular shuttles powered by sunlight. One of the global issues is the energy crisis, and creating these artificial nanomachines could prove potentially to solve many problems. These molecular shuttles can absorb energy in the form of photons and cause reversible chemical reactions that effectively eliminate waste products. The basics of the functions of these shuttles are that they consist of electron donors and acceptors and due to the structure of the rotaxane it is able to make a photon induced electron-transfer to bring them into excited states. Since 1985 a team of scientists, H. W. Kroto, R. F. Curl and R. E. Smalley, had discovered an allotrope of carbon which they had called Fullerene or a Bucky ball as the molecule (in Figure 3) 4 (carbon - 60) resembled a football. This discovery prompted chemists that potentially carbon could be arranged in such ways to exhibit particular properties that emulate natural substances in terms of their electrical, thermal and tensile strength properties. This Fullerene molecule was discovered after examining the byproducts of laser - vapourised graphite in an inert atmosphere. Fullerene molecules can be implemented into organic solar cells [5] where it can be used as a semiconductor because of its electrical properties. It has shown to increase the efficiency of the device, and with the introduction of Fullerene Carbon-70, it has improved even better. These molecules are also known as powerful antioxidants and many chemists want to explore the ways in which it can treat many incurable diseases such as Alzheimers or even cancer. It has the ability to prevent cell damage by tackling the absorption of free radicals which can trigger these conditions. So far, Fullerene has been used in skin care products has it has proven to be a better antioxidant than vitamin E. The toxicology tests on Fullerene have shown no harmful effects, which is a great benefit to many pharmaceutical companies. A powerful application of arranging carbon into different allotropes is the design and construction of carbon nanotubes, discovered in 1991. (Figure 2) 5 The remarkable features of these nanotubes include having the highest strength to weight ratio known to man. It has a Youngs Modulus of over 1 Tera Pascals and with an estimated tensile strength of 200 Giga Pascals. Its highly regarded properties and could in fact lead civilisation to design new infrastructures with greatly enhanced stability and in the electronics industry, can be used for better computing power. These nanotubes are hexagonal-shaped arrangements of carbon atoms on a sheet and then rolled into tubes. They can even be made with varying thicknesses and even have a nanotube with different layers of nanotubes within. Carbon nanotubes can be grown through a chemical vapour deposition process, which uses a metal catalyst such as gold, in a vapour of carbon rich gas under high temperature. The gas reacts with the catalyst and eventually carbon deposits builds up. They are extremely thin with the thickness of just a few atoms and can be made with a length of a few centimetres, making their length to thickness ratio of the order of millions. One of the most interesting features is that it has superior electrical and thermal properties that rival the best silicon semiconductor technology. It can conduct electricity just as well as copper and transfer heat like diamond. Carbon nanotubes have numerous applications including the construction sports equipment such as bicycle components and tennis rackets, proving to be a cost effective way of reducing the weight and increasing the strength and stability to improve performance. Such technology is also used in medicine where the nanotube acts like a needle where it can penetrate at a cellular level to deliver drugs directly into diseased cells. The carbon nanotubes can also be used in molecular manufacturing where molecular
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Image Credit: http://www.ch.ic.ac.uk/local/projects/unwin/Fullerenes.html Image Credit: http://www.gkdidyouknow.com/wp-content/uploads/2011/06/carbon-nanotubes.png

fabricators have the ability to build products atom by atom using raw materials sup- plied. The products built would have greater enhanced performance because the finished product is finely tuned from the nanoscale range. The products that nanotechnology offers would help create new businesses and would lower the prices of products such as the bicycle components. Only as recently in 2010, researchers at MIT have used carbon nanotubes to drastically improve the performance and charge capacity of a lithium battery [6]. Due to the large surface area to volume ratio of carbon nanotubes, scientists were able to make the battery store more charge by changing the cathode terminal of the battery and replacing it with layers of nanotubes. The result compared to a normal lithium battery, were an increased capacity by a third and an output power ten times higher. Such results lead many scientists questioning what potential such an improvement in battery performance could achieve. To manipulate and change the structure of carbon nanotubes, an Atomic Force Microscope (AFM) is used. This device can scan for high-resolution topography to locate a specific nanotube and the very tip of its cantilever can actually be used to move the carbon nanotubes. Van der Waals forces between the surface and the nanotube keep hold of its position so that it does not retain its original shape. One of the most ambitious and exciting goal for using nanotubes is to build space elevators [8] which are mammoth structures extending thousands of miles out into space that can act as a transportation system sending people, payloads and energy to and from Earth. These space elevators would be made possible by carbon nanotubes because of its high strength to weight ratio that would otherwise cause it to collapse under its own weight. The very idea was originally thought in 1895 by Konstantin Tsiolkovsky, a Russian rocket scientist. Looking at the Eiffel tower he had imagined the structure to be like a celestial castle, which he envisioned that such a tower could extend reaching out in space. The structure of the tower would need to have a centre of mass at geostationary orbit so that the structure is in synch with the Earths orbit. The problems with nanotubes at the moment are they can be grown to just a few centimetres in length in small quantities, there needs to be a method for a mass production of these materials to build such an elevator. However there is a problem that producing carbon nanotubes of a certain type in factories also present a health hazard to workers if they are inhaled or pass through the skin, as they have a level of toxicity that is similar to asbestos. If inhaled, some nanotubes are able to induce a certain type of cancer called mesothelioma. Recently Nanoshell Assisted Tumor Ablation was discovered by researchers a Rice University in 2005. These nanoshells [7] were used for a minimally invasive cancer therapy. The researchers Professor N. Halas and J. West discovered that taking nanoparticle of silica and coating it with gold nano-particles enables it to absorb and scatter different wavelengths of radiation depending on their size and thicknesses. They had realised that by adjusting the dimensions of these nanoshells they could in fact use a photothermal treatment of cancer. These particles would then be combined with hormones and peptides that are injected into the bloodstream to detect and accumulate in cancer cells. This happens because the blood vessels near tumours are very weak and poorly developed, and would cause the particles to leak to the tumour. The nanoshells can then be heated at a high temperature with a high-powered infrared laser to eventually destroy cancer cells. The technique to do this is called optical coherence tomography where a low power infrared laser is shone on tissue, and since the nanoparticles scatter that light it can be measured to locate the cancer cells. Once the cancer cells are located, because of the structure of the nano-particles, it would absorb specific wavelengths and only the cancer cells would be affected. The neighbouring healthy tissue will not induce much of a temperature increase since the heating is localised.

This technology has been tested on tumours in mice and the results have proven to be very promising, as the nanoshell treatment has increased the survival time of mice. It has almost completely eradicated the cancer cells and after several weeks there seems to be no sign of cancer cells returning. However there are drawbacks into this treatment as this therapy would only work on tumours near the surface of the skin, for tumours deep within the body would require more penetrating radiation but that would mean the nanoparticles would have to be constructed to absorb those particular wavelengths. Scientists have known that nano-silver [9] has antibacterial properties that are able to inhibit and destroy the growth of bacteria. These particles are vastly different com- pared to normal silver because of their larger surface area to volume ratio. Nano-silver particles can provide a anti-microbial coating which is useful in many products such as footwear, bandage dressings, cosmetics and cleaning cloths. Basically any applications which require clean surfaces to prevent the spread of bacteria. The nano-silver is known as a natural anti-microbial, the silver ions have the ability to disable many of the enzymes that bacteria or microbes use for oxygen. This feature would stop their respiration and hence suffocates them. But the properties of silver nanoparticles presents a risk to the environment as the ever growing use of silver nanoparticles in products presents a problem since the silver can also kill benign bacteria that remove ammonia, if washed into wastewater treatment systems. It is also not known what the long-term effects on human health are from a prolonged exposure to these nanoparticles, so much research is currently under development in nanotoxicology. The 20th century has been a revolutionary era of the electronic age. Since the birth of quantum mechanics, a new hidden world of the very small exists that contains extraordinary science waiting to be discovered. Scientists since then concentrated on studying objects on an ever-smaller scale. Richard Feynman who revised many of the theories of quantum mechanics and in quantum electrodynamics had a vision in his talk of Theres Plenty of Room at the Bottom, that atoms can be manipulated artificially to any arrangement desired by methods of synthetic chemistry. Nanotechnology is growing astronomically as the research and development continues. It is progressing at such a rate that new discoveries are being made everyday and no one can predict its future possibilities. Eric Drexlers book The Engines of Creation is ever becoming truer with his vision of molecular nanotechnology and descriptions of positive benefits to society. Throughout this essay examples of the developments of nanoscience of interest to chemists in the chemical industry, include the development of molecular devices and machines that are able to process information, transfer energy and perhaps form assemblers to construct on the nanoscale level. Advances in nanoscience have remarkably seen developments in cancer therapy and in health and medicine, and also improvements to engineering with the introduction of carbon nanotubes. It is with hindsight that such technology will be able to revolutionise businesses and even create new ones within its field. A large investment into such technology could in fact have the potential to solve some of the major problems facing the world today: energy, water, food, health and the environment.

Figures

Figure 1: Computer model of a Rotaxane (left) and a Catenane (right).

Figure 2: Computer model illustrating carbon nanotubes.

Figure 3: Computer model illustrating the Carbon-60 Fullerene molecule.

Bibliography

[1] Theres Plenty of Room at the Bottom R.Feynman, American Physical Society Lecture, 1959 [2] Engines of Creation - The Coming Era of Nanotechnology E.Drexler, Non Basic Stock Line, 1 Sep. 1988 [3] Molecular devices and machines V. Balzani et al, nanotoday, April 2007, Vol. 2, No. 2 [4] Artificial nanomachines based on interlocked molecular species: recent advances V. Balzani, A. Credi et al, Chem. Soc. Rev., 2006, Vol. 35, 1135-1149 [5] http://www.nano-c.com/fullereneapp.html [6] http://www.scientificamerican.com/article.cfm?id=carbon-nanotubes-boost-power-oflithium-battery [7] Nanoshell-assisted cancer therapy: Targeted photothermal tumor ablation A.R.Lowery, PhD Thesis, Rice University, 2007 [8] http://science.nasa.gov/science-news/science-at-nasa/2000/ast07sep_1

[9] http://www.sigmaaldrich.com/materials-science/nanomaterials/ silvernanoparticles.html

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