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The pealet mM Im poakele $394 " ehenraceriehe alosoaph, yh fe plots om vem uted._ OF kk ™? = N umoporh ae ae S{ Ge ain si iy subjetea te om ; ea Geum bse qin w, Si thy ry SET Sy eee Sts (Shar hy = entry? 5} meron. Comore Aplesabis Explosion pthim we fexge % chuta, oo v aopicl 5 ote ule place. Datistaibuhe sy Berl) seclae QDute fo owe ALD biti cheyo , phn e6 4 peat ye" covtom bic Asprbasm oy otory on te bading ee amy ober, Te ond otort yor expo witt gael ya keno velsubes . THe phememres Combs bt en losin:' = TOUETA eee: Applic atten® Of, Naww makovals Some nanomaterials are harder than conventional materials. Cutting tools and drills made of nanocrystalline materials, such as tungsten car- bide, tantalum carbide, and titanium carbide, are much harder, much more wear-resistant, erosion-resistant, and last longer than their con- ventional (large-grained) counterparts. They also enable the manufac- turer to machine various materials much faster, thereby increasing Productivity and significantly reducing manufacturing costs. Nanocrystalline silicon nitride (Si;N,) Bigure-3-9) and silicon carbide (SiC), have been used in automotive applications as high-strength springs, ball bearings, and valve lifters, because they are readily machineable and have excellent physical, chemical, and mechanical Properties. They are also used as components in high temperature rnaces. On the other hand, some nanomaterials are softer than conven- onal materials. Conventional ceramics are very hard, brittle, and dif- ficult to machine. Zirconia, ZrO,, a hard, brittle ceramic, has even been rendered Superplastic by ‘nanocrystalline grains. It can be deformed to great lengths (up to 300% of its original length). Nanocrystalline ceramics can be pressed and sintered into various shapes at significantly lower temperatures, whereas it would be very difficult, if not impossible, to Press and sinter conventional ceramics even at high temperatures, PHOSPHORS The resolution of a television or a monitor depends greatly on the size of the pixel. These pixels are essentially made of materials called phos- Phors, which glow when struck by a stream of electrons inside the cath- ode ray tube (CRT). The resolution improves when the pixels, or the Phosphors, are smaller. Nanocrystalline zinc selenide, zinc sulfide, cad- mium sulfide, and lead telluride synthesised by the sol-gel technique improve the resolution of monitors. The use of nanophosphors would reduce the cost of making high resolution televisions. Carbon-nan- ¢ 4) are_also candidates, Similar arguments apply to low ° ; cost-flat-pancl-displays.BATTERIES : Nanocrystalline materials synthesised by sol-gel techniques are used a separator plates in new generation batteries because of their aeroge structure, which can hold considerably more energy than convention- al plates. Nickel metal hydride (Ni-MH) batteries made of nanocrys- talline nickel and metal hydrides require far less frequent recharging and last much longer. HIGH POWER MAGNETS z ‘The strength of a magnet increases with increased surface area per unit volume. It has been shown that magnets made of nanocrystalline yttri- um-samarium-cobalt nanoparticles possess very unusual magnetic properties due to their extremely large surface area. Typical applica- tions for these high power rare-earth magnets include quieter sub- marines, automobile alternators, land-based power generators, motors for ships, ultra-sensitive analytical instruments, and magnetic resonance imaging (MRI) in medical diagnostics. MOTOR VEHICLES AND AIRCRAFT Motor cars waste significant amounts when thermal energy generated by the engine is lost. This is especially true in the case of diesel engines. To prevent this waste, the engine cylinders (liners) are currently coat- ed with nanocrystalline ceramics, such as zirconia and alumina, so that . they retain heat much more efficiently and resuic in complete and effi- cient combustion of the fuel. In aircraft, fatigue strength is critical. The fatigue strength increas- es with a reduction in the grain size of the material. Nanomaterials pro- vide such a significant reduction in the grain size over conventional materials that the fatigue life is increased by as much as 300 per cent. Furthermore, components made of nanomaterials are stronger and can operate at higher temperatures. This means that aircraft can fly faster and more efficiently using the same amount of aviation fuel. In space- craft, elevated-temperature strength is crucial for components such as rocket engines and thrusters, and particularly for surface material that will be in contact with the atmosphere on re-entry. Likewise, the amount of fuel that can be carried on board is crucial so the ratio of fuel to total weight is important. Nanomaterials, such as nanocrys- talline tungsten-titanium diboride-copper composites, are potential candidates for increasing combustion efficiencies and hence reducing fuel use in these applications. MEDICAL IMPLANTS For an implant to effectively mimic a natural human bone, the sur- rounding tissue must penetrate the implants to give the implant the strength it needs. Since conventional materials are relatively impervious,4 cig seetey Gane uae @te UL as ELTEC- tive. Furthermore, these metal alloys wear out quickly, necessitating fre- quent, and often very expensive, surgery. However, nanocrystalline zirconia ceramic is hard, wear-resistant, corrosion-resistant (biological fluids are corrosive), and biocompatible. Nanoceramic aerogels can also withstand up to 100 times their weight. The products last longer and the patient needs less frequent implant replacements. This leads to a sig- nificant reduction in surgical expenses. Nanoceramics can also be made of apatite, a calcium phosphate material from which bone is derived, thereby mimicking nature’s own process [17, 18]. The sol-gel prepared nanottania (TiO,) forms a chemical bond with the living bone in the body, although the bond is not very strong. However, impregnating the titania gel with hydroxyapatite is a promising way to increase its bioac- tivity. Nanocrystalline silicon carbide (SiC) is a candidate material for artificial heart valves primarily due to its low weight, high strength, extreme hardness, wear resistance, inertness (SiC does not react with biological fluids), and corrosion resistance. OTHER MEDICAL USES Gel technology has also been used in DNA separations. There has been a quest for an artificial gel that would replace the organic gels used to Separate fragments of DNA for analysis. Traditionally this has been done by a process called gel electrophoresis. Enzymes are used to chop DNA strands into many short pieces of varying length. The sample is placed at one end of a column of organic gel and an electric field is applied to force the DNA to move through the gel. As they slowly pass through the tiny pores of the material, DNA fragments of different lengths move at different speeds and eventually collect in a series ‘of bands as a ladder-like structure that can be photographed using fluo- rescent or radioactive tags. The resulting image is a list of the lengths of the fragments, from which genetic information can be determined. Silicon-based nanostructures with pores comparable to the size of a large DNA molecule can also perform these separations, These meth- ods could also be applied to the study of other lar 'ge organic molecules, including proteins, carbohydrates and lipids, for many of which clec- trophoresis is useless. As noted, nanoparticles of iron can be used to form strong mag- nets. However, the size of the particle can be Put to good use medically in other ways. Nanoparticles of the iron oxide Fe,O, have-diameters in the 5-100 nm range. These particles are magnetic and thus can be fol- lowed by a magnet in the body using nuclear magnetic resonance imaging (this is known as magnetic resonance imaging (MRI) so ‘that the use of the word ‘nuclear’ does not scare the patient). In MRI, pro- tons are excited with short pulses of radio-frequency radiation. The free induction decay as the Protons relax is measured and deconvolutedNanoparticles are commonly used for laboratory studies as well as in vivo. Tagged to a biomaterial of interest they can be dispersed effec- tively, coated with a monoclonal antibody for a cell-surface antigen. The antibody-tagged particles are then incubated with a solution con- taining the cells of interest. The microparticles bind to the surfaces of the desired cells, and these cells can then be collected in a magnetic ficld. Methods of this type have been used to isolate or remove numer- ‘ous cell types, including lymphocytes (cells that control immune response) and tumour cells. : Particles with truly nanoscopic dimensions have also beén used in the ‘First Response’ home pregnancy test, which uses conventional tnicrometre-cired latex particles in conjunction with gold nanoparticles (less than 50 nm diameter). Gold nanoparticles have a characteristic Visible absorption band called the plasmon resonance absorpuoh,. - which makes them pink (plasmons are described in Chapter 7). The1 sition frets P porckion Q Dune yp. ‘That a plasma is an ionised gas. A plasma is achieved by making a gas conduct electricity by providing a potential difference across the two clectrodes so that the gas yields up its electrons and thus jonises. In a vacuum or in an inert gas the electrodes can be made volatile. Heat is produced and other material can be volatilised and ionised using this heat, Plasma arcing has been important in forming carbon nanotubes. Chemical vapour deposition is a method of making nanoparticulate material from the gas phase. Material is heated to form gas and then allowed to deposit as a solid on ‘a surface, usually under vacuum. There may be direct deposition or deposition by chemical reaction to form a new product that differs from the material volatilised. Chemical vapour deposition is particularly usefal for making aligned materials on surfaces The sol-gel process, as the name implies, involves the evolution of networks through the formation of a colloidal suspension (sol) and gelation of the sol to form a network in,a continuous liquid phase (gel). The precursors for synthesising these colloids consist of ions of a metal or metalloid element surrounded by various reactive ligands. Sol-gel processes can preserve the voids in solution in the solid state thereby producing nanoholes. In nanoclectrodeposition, the aim is to place only a single layer or more of coverage on a surface in a very controlled way. Nanostructured films of platinum can be produced by‘rop with gravity force on’ to.a solid:enclosed in the drum. Ball - milling breaks down the structure into nanocrystallites. Ball milling 5 _Inball milling, small balls are allowed to. rotate around.a drum and is the preferred method of preparing nanometal oxides. Nanoparticles can also, be: prepated by altering the poresspaces in phyllosilicates by’ urfactants and then ‘filling. them if required. Pa 2 Nanomaterials. have found -applications as insulators, batterics, machine tools, phosphors and magnets. They are used in aircraft, » building structures and medicine.10.4 NANOMEDICINE [9, 10] Medicine is concerned with diagnosis and cure. A cure may only need to be short term, such as during the process of an operation or until nat- ural healing can take place. Nanomedicine may have some potential in oe of these areas, but in the short term it may be used primari in senosis. This be done using nanoreceptors ach wo cuisedisend bide ie 6. Instruments that are used in nandmedicine could well be bars Ss material because of the obvious congruency. Nanoreceptors cific te ie identify trace amounts of biological material that are spe- 4 parca ic picrace ofa particular virus or bacterium, or which detect These a aL ody malfunction, such as brain abnormality or organ stress. ja ae id be based on electrical devices built by tethering a molecu- eae deheeahie membrane so that a change in ion concentration cre- OF thotae =f ¢ electrical current, as described in Chapter 6. Hundreds iets nds of these devices could be present in a single probe, each wit a specific electrical signature so that a read-out of pathogen versus concentration could be determined. Any particular body fluid could be studied. In the doctor’s surgery or a forensic laboratory it would be sali- va, sweat, urine, blood, sperm or vaginal fluid. Many of the potential advantages in diagnosis can be achieved by using pre-formed biological material. Many of these materials were dis- cussed in Chapter 6. Membranes in particular offer great advantages, however there are lots of other useful concepts. Understanding the mechanism that makes human cells stick to other surfaces could help to produce better medical devices, Nanostructures could form novel bio- aterial coatings, cither to prevent cells from binding to surfaces (for instance, to prevent blood clotting), or to improve their adhesion and biocompatibility for repairing skin and other damaged tissues. The liv- ing cells of the human body are very complex, and many of the effects of interactions or coupling of cells are presently unknown. In such bio- logical systems, cells arc able to stick to other surfaces. The degree es on both the structure of the material’s surface at the . d : [note ano the characteristics of the cells. Biomaterial coatingswould offer better biocompatibility for applications in the field of bio- medical devices used for common medical procedures and treatments (such as the transport of blood and removal of other body fluids via catheters); and for the production of improved biomaterials used in tis: sue engineering and wound healing. Nanotechnology is of particular value for. biomedical applications since devising ways to prevent cells from binding to a surface is an important feature of many medical devices. A low adhesion component is required for hollow devices used to transport biological fluids such as blood and urine. The low adhesion properties prevent the blood clotting as it passes through the tube, and stop the tube becoming overgrown with cells. Such properties also help to prevent bacterial contamination. The surfaces of membranes, which are now altered by drugs, could be altered by nanomanipulation of the membranes by adding nanocoatings. Damaged tissues often stick to other tissue surfaces. This can cause post-operative pain when the tissues . that are stuck together are torn apart by the patient’s movements. The risk of such pain can be reduced significantly if tissue adhesion is restrict- ed by applying a biodegradable surface coating to the damaged tissue or organ. Nanocoatings arc also invaluable in situations where high ache- sion is required to help tissues stick together during healing. Examples include skin, muscle and bone repair. The use of nanosechnology in diagnos! ould also be achieved by mechanical nanorobots. However Chaptei shown _us that these afe stil Tar off. The most likely scenario is chemical robots. These are effectively smart i DNA sequences and repair brain or oth understand more biochemistry, larger self- defines the field of supramolecular chemistry) will undertake this frhc- chines, One part will be used for penetra- emoval or destruction. These inside giant fullerene oF tion, another for ac ner selF-assemblies of molecules may be nanotube capsules ible in bi Freitas [9] has discu: ‘a_respirc This is an artificial red blood cell about the size of a_ bacterium, which iclivers more oxygen than a normal one, and would be useful for treat- ing people with poor lung capacity. The physical size of the device is easy to specify because respirocytes miist have ready access to all tissues by blood capillaries. They must be no larger than 8 am in diameter, but they may be as small as natural red blood cells, which are 7.82 xm x 2.58 ym in diameter. This is not nanosized. However, if built from molecular parts these artificial cells would be comprised of a iumber of nanomachines. Respirocytes may be fuelled’ by glucose in the blood. Binding sites for glucose are common in nature. For example, cellular energy metab- olism starts with the conversion of the 6-carbon glucose to two 3-\s carbon fragments (pyruvate or lactate), the first step in glycolysis. This is catalysed by the enzyme hexokinase, which has binding sites for both glucose and adenosine triphosphate (ATP). Another common cellular mechanism is the glucose transporter molecule, which carries glucose across cell membranes and contains several binding sites. Freitas sug- gests these could be used in membrane structure to form a respirocyte. The biochemistry of respiratory gas transport in the blood is well understood. In brief, oxygen and carbon dioxide are carried between the lungs and the other tissues, mostly within the red blood cells (ery- throcytes), Haemoglobin, the principal protein in the red blood cell, combines reversibly with oxygen, forming oxyhaemoglobin. According to Freitas, at human body temperature, the haemoglobin in one litre of blood holds 200 cmé of oxygen. The key to successful respirocyte function is an active means of con- veying gas molecules into and out of pressurised microvessels. Molecular sorting rotors have been proposed that would be ideal for this task, how- ever, they may look more like a nanofilter (Chapter 3) and a biological nanopump (Chapter 6). Moiccular sorting rotors can be designed from structures that are generated by producing nanosized holes in plastics (Chapter 3). Instead of filling them with gold or other materials, they would be used as filters. In the model proposed by Freitas however, each rotor has binding site ‘pockets’ along the rim, exposed alternately to the blood plasma and interior chamber by the rotation of a disk, which com- poses the rotating part of the nanomachine. Each pocket selectively binds a specific molecule when exposed to the oxygen or carbon dioxide source. Once the binding site rotates to expose it to the interior cham- ber, the bound molecules are forcibly ejected. Freitas points out [9] that artificial reversible oxygen-binding mol- ecules have been studied by a number of scientists trying to make arti- ficial blood, including coba!t-based porphyrins such as coboglobin (a cobalt-based analogue to hacmoglobin) and cobaltodihistidine. Other candidates for this application have included other metallic porphyrins simple iron-indigo compounds; iridium complexes, such as chloro-car- bonyl-bistriphenylphosphinc)-iridium; a simple cobalt/ammonia complex; zeolite-bound divalent chromium; and non-porphyrin iron complexes. Unlike haemoglobin, haemocyanin, haemerythrin and coboglobin are not poisoned by carbon monoxide. It is likely therefore that the technology for respirocytes will be structured so they cannot be poisoned. It is possible that respirocytes might transfer oxygen or carbon dioxide or both. Many proteins and enzymes have binding sites for carbon dioxide. For example, haemoglobin reversibly binds carbon dioxide, forming carbamino haemoglobin. A zinc enzyme present in red blood cells, carbonic anhydrase, catalyses the hydration of dis- solved carbon dioxide to bicarbonate ion. In photosynthesis, carbondioxide is added to a five-carbon sugar, ribulose biphosphate carboxy J fart atest potential nanoc lase, using chlorophyll. This is probably, pe eet ses problems. The cological advance: it may help to re 2p aa “Ae effect of all the green porate one ce es extract the biological machine leaves on Earth, we : it id let it intact, place it on a surface, reproduce it many, many anal one ee work. It will need to be regulated, or it may starve n: carbon dioxide. eats ‘ A built-in computer or related control device is necessary 10 Beds precise control of respiratory gas loading and unloading ee we ae cs tions in respirocytes or photosynthesis machines. This must oe are modated in the j.m?-sized device. Freitas [9, 10] believes a 10* bit/sec computer can probably meet all computational requirements, given the simplicity of analogous chemical process control systems in factory set- tings. This is not much, considering that even the early PCs typically had access to 10° bits (0.1 megabyte) of external floppy drive memory. We have seen in Chapter 8 how quantum computers could do this with case, but we are a long way from miniaturising such a device. A chemi- cal computer (Chapter 5) would be sufficiently miniature. Some studies have already investigated the biocompatibility of medical nanorobots [11, 12]. In particular Freitas [9,10] has discussed whether they will be rejected or not. The most common cause of rejec- tion for material that does not need to be incorporated in body tissue, such as transplant organs, is an effect on bodv temperature. Heating blood above 47°C produces damaged erythrocytes. High temperatures also affect other organs, such as the brain, People have been known to “go troppo’ when they are suffering from hyperthermia. Hyperthermia is a heating effect that may develop during periods of intense physical exertion, dehydration, and immersion in hot fluids. It may be due to heat thrown out by respirocytes. 3 Another cause of overheating is when the body deliberately increas- es its temperature. This is called fever. Fever is a natural self-defence mechanism intended to make the host less hospitable to microscopic invaders, The intact control mechanisms of thermoregulation act to raise body temperature up to the new set point, then maintain the ele- vated systemic temperature. Fever is triggered by the release of fever- producing substances from cells of the immune system into the bloodstream. Can nanorobots act as pyrogens, inducing fever? The evidence is variable. Some materials are satisfactory and some are not. For exam- ple, latex particles do not induce fever and the simple building mate- rials of the anticipated nanorobots, such as diamond, fullerenes, or graphite, are inert. Carbon powder has been used in nasal provocation tests without eliciting fever and it has also been used with tellurium for radioactive mapping of the lungs. With rare exceptions, bulkTeflon appears non-pyrogenic, although perfluorocarbon emulsion can cause cutaneous flushing and fever at low doses and “polymer fume fever’ or ‘Teflon fever’ results when Teflon combustion products are inhaled. Other particulates are less inert. Metal fume fever (due to zinc oxide inhalation) is well known: excess trace elements such as copper and zinc can induce fever. Silica crystals and various low-solubility sub- stances that crystallise in the human body can trigger fever. For exam- ple, monosodium urate monohydrate crystals, which are deposited during gout, cause fever, Feyer has been reported from kidney stones, from calcium oxalate bladder stones, from calcified lymph-node stones in broncholithiasis, and from calcified salivary gland stones. Cholesterol crystals deposited as gallstones may cause fever, as may cholesterol crystals in the blood. i Even if this is a problem, research into new materials will solve it. Morcover, there are many medical areas where the possibilities of rejec- tion are not as crucial, such as nanodentistry and nanocosmetics. There are other. applications for nanamachines, such as in nitrogen fixation. It is well known that legume bacteria and soil microorganisms, “such as Azotobacter and algac (Anabaena cylindrica) can fix nitrogen. All we need to do is decouple this nanomachine from the organism and put it to use in the same way as the photosynthetic machine, and we can use the product to make all the proteins we need.PEK Carbon Clusters 79.6.1, Small Carbon Clusters Laser evaporation of a carbon substrate using the apparatus shown in Fig. 79.1 in a pulse of He gas is used to make carbon clusters, The neutral cluster beam is photoionized by & UV laser and analyzed by a mass spectrometer. Fig. 79.11 shows the mass spectrum of carbon clusters. For the number of atoms N less than 30, there are clusters of every N, although some are more prominent than others (Calculatigns of she i i@R'signal ——> 40. 60 80 100 Cluster size N —>- 3’ respectively. closed structures have angles between the ‘cluster composed of 60 atoms shows the highest intensity in the mass spectrum and hence the most stable. ER ; "79.6.2. Discovery of Ceo The evidence for the existence of a molecule containing 60 carbon atoms was first found while measuring the intensity of light coming from stars at different wavelengths. A pronounced reductionCHNOLOGY pe Ie st . 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