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Sunday, July 1, 2018

Biomimetics

From Wikipedia, the free encyclopedia
 
burr
The tiny hooks on bur fruits ...
velcro tape
... inspired Velcro tape.










Biomimetics or biomimicry is the imitation of the models, systems, and elements of nature for the purpose of solving complex human problems.[1] The terms "biomimetics" and "biomimicry" derive from Ancient Greek: βίος (bios), life, and μίμησις (mīmēsis), imitation, from μιμεῖσθαι (mīmeisthai), to imitate, from μῖμος (mimos), actor. A closely related field is bionics.

Living organisms have evolved well-adapted structures and materials over geological time through natural selection. Biomimetics has given rise to new technologies inspired by biological solutions at macro and nanoscales. Humans have looked at nature for answers to problems throughout our existence. Nature has solved engineering problems such as self-healing abilities, environmental exposure tolerance and resistance, hydrophobicity, self-assembly, and harnessing solar energy.

History

One of the early examples of would-be biomimicry was the study of birds to enable human flight. Although never successful in creating a "flying machine", Leonardo da Vinci (1452–1519) was a keen observer of the anatomy and flight of birds, and made numerous notes and sketches on his observations as well as sketches of "flying machines".[3] The Wright Brothers, who succeeded in flying the first heavier-than-air aircraft in 1903, allegedly derived inspiration from observations of pigeons in flight.[4]

During the 1950s the American biophysicist and polymath Otto Schmitt developed the concept of "biomimetics".[5] During his doctoral research he developed the Schmitt trigger by studying the nerves in squid, attempting to engineer a device that replicated the biological system of nerve propagation.[6][need quotation to verify] He continued to focus on devices that mimic natural systems and by 1957 he had perceived a converse to the standard view of biophysics at that time, a view he would come to call biomimetics.[5]
Biophysics is not so much a subject matter as it is a point of view. It is an approach to problems of biological science utilizing the theory and technology of the physical sciences. Conversely, biophysics is also a biologist's approach to problems of physical science and engineering, although this aspect has largely been neglected.
— Otto Herbert Schmitt, In Appreciation, A Lifetime of Connections: Otto Herbert Schmitt, 1913 - 1998
In 1960 Jack E. Steele coined a similar term, bionics, at Wright-Patterson Air Force Base in Dayton, Ohio, where Otto Schmitt also worked. Steele defined bionics as "the science of systems which have some function copied from nature, or which represent characteristics of natural systems or their analogues".[2][7] During a later meeting in 1963 Schmitt stated,
Let us consider what bionics has come to mean operationally and what it or some word like it (I prefer biomimetics) ought to mean in order to make good use of the technical skills of scientists specializing, or rather, I should say, despecializing into this area of research
— Otto Herbert Schmitt, In Appreciation, A Lifetime of Connections: Otto Herbert Schmitt, 1913 - 1998
In 1969 Schmitt used the term “biomimetic“ in the title one of his papers,[8] and by 1974 it had found its way into Webster's Dictionary, bionics entered the same dictionary earlier in 1960 as "a science concerned with the application of data about the functioning of biological systems to the solution of engineering problems". Bionic took on a different connotation when Martin Caidin referenced Jack Steele and his work in the novel Cyborg which later resulted in the 1974 television series The Six Million Dollar Man and its spin-offs. The term bionic then became associated with "the use of electronically operated artificial body parts" and "having ordinary human powers increased by or as if by the aid of such devices".[9] Because the term bionic took on the implication of supernatural strength, the scientific community in English speaking countries largely abandoned it.[10]

The term biomimicry appeared as early as 1982.[11] Biomimicry was popularized by scientist and author Janine Benyus in her 1997 book Biomimicry: Innovation Inspired by Nature. Biomimicry is defined in the book as a "new science that studies nature's models and then imitates or takes inspiration from these designs and processes to solve human problems". Benyus suggests looking to Nature as a "Model, Measure, and Mentor" and emphasizes sustainability as an objective of biomimicry.[12]

Commercial applications

Fabrication

Electron micrograph of rod shaped TMV particles.

Biomorphic mineralization is a technique that produces materials with morphologies and structures resembling those of natural living organisms by using bio-structures as templates for mineralization. Compared to other methods of material production, biomorphic mineralization is facile, environmentally benign and economic.[13]

Display technology

Morpho butterfly.
Vibrant blue color of Morpho butterfly due to structural coloration

Morpho butterfly wings contain microstructures that create its coloring effect through structural coloration rather than pigmentation. Incident light waves are reflected at specific wavelengths to create vibrant colors due to multilayer interference, diffraction, thin film interference, and scattering properties.[14] The scales of these butterflies consist of microstructures such as ridges, cross-ribs, ridge-lamellae, and microribs that have been shown to be responsible for coloration. The structural color has been simply explained as the interference due to alternating layers of cuticle and air using a model of multilayer interference. The same principles behind the coloration of soap bubbles apply to butterfly wings. The color of butterfly wings is due to multiple instances of constructive interference from structures such as this. The photonic microstructure of butterfly wings can be replicated through biomorphic mineralization to yield similar properties. The photonic microstructures can be replicated using metal oxides or metal alkoxides such as titanium sulfate (TiSO4), zirconium oxide (ZrO2), and aluminium oxide (Al2O3). An alternative method of vapor-phase oxidation of SiH4 on the template surface was found to preserve delicate structural features of the microstructure.[15] A display technology ("Mirasol") based on the reflective properties of Morpho butterfly wings was commercialized by Qualcomm in 2007. The technology uses Interferometric Modulation to reflect light so only the desired color is visible in each individual pixel of the display.[16]

Possible future applications

Leonardo da Vinci's design for a flying machine with wings based closely upon the structure of bat wings

Biomimetics could in principle be applied in many fields. Because of the complexity of biological systems, the number of features that might be imitated is large. Biomimetic applications are at various stages of development from technologies that might become commercially usable to prototypes.[17]

Prototypes

Researchers studied the termite's ability to maintain virtually constant temperature and humidity in their termite mounds in Africa despite outside temperatures that vary from 1.5 °C to 40 °C (35 °F to 104 °F). Researchers initially scanned a termite mound and created 3-D images of the mound structure, which revealed construction that could influence human building design. The Eastgate Centre, a mid-rise office complex in Harare, Zimbabwe,[18] stays cool without air conditioning and uses only 10% of the energy of a conventional building of the same size.

In structural engineering, the Swiss Federal Institute of Technology (EPFL) has incorporated biomimetic characteristics in an adaptive deployable "tensegrity" bridge. The bridge can carry out self-diagnosis and self-repair.[19]

Technologies

Practical underwater adhesion is an engineering challenge since current technology is unable to stick surface strongly underwater because of barriers such as hydration layers and contaminants on surfaces. However, marine mussels can stick easily and efficiently to surfaces underwater under the harsh conditions of the ocean. They use strong filaments to adhere to rocks in the inter-tidal zones of wave-swept beaches, preventing them from being swept away in strong sea currents. Mussel foot proteins attach the filaments to rocks, boats and practically any surface in nature including other mussels. These proteins contain a mix of amino acid residues which has been adapted specifically for adhesive purposes. Researchers from the University of California Santa Barbara borrowed and simplified chemistries that the mussel foot uses to overcome this engineering challenge of wet adhesion to create copolyampholytes,[20] and one-component adhesive systems[21] with potential for employment in nanofabrication protocols.

Spider web silk is as strong as the Kevlar used in bulletproof vests. Engineers could in principle use such a material, if it could be reengineered to have a long enough life, for parachute lines, suspension bridge cables, artificial ligaments for medicine, and other purposes.[12] Other research has proposed adhesive glue from mussels, solar cells made like leaves, fabric that emulates shark skin, harvesting water from fog like a beetle, and more.[18] Murray's law, which in conventional form determined the optimum diameter of blood vessels, has been re-derived to provide simple equations for the pipe or tube diameter which gives a minimum mass engineering system.[22] Aircraft wing design [3] and flight techniques[23] are being inspired by birds and bats.

The BionicKangaroo reproduces the jumping locomotion of a kangaroo, bouncing to recover much of the energy of each jump.

Biorobots based on the physiology and methods of locomotion of animals include BionicKangaroo which moves like a kangaroo, saving energy from one jump and transferring it to its next jump,[24] and climbing robots,[25] boots and tape[26] mimicking geckos feet and their ability for adhesive reversal. Kamigami Robots, a children's toy, mimic cockroach locomotion to run quickly and efficiently over indoor and outdoor surfaces.[27] Nanotechnology surfaces that recreate properties of shark skin are intended to enable more efficient movement through water.[28] Tire treads have been inspired by the toe pads of tree frogs.[29] The self-sharpening teeth of many animals have been copied to make better cutting tools.[30] Protein folding has been used to control material formation for self-assembled functional nanostructures.[31] The structural coloration of butterfly wings has been adapted to provide improved interferometric modulator displays and everlasting colours.[32] New ceramics copy the properties of seashells.[33] Polar bear fur has inspired the design of thermal collectors and clothing.[34] The arrangement of leaves on a plant has been adapted for better solar power collection.[35] The light refractive properties of the moth's eye has been studied to reduce the reflectivity of solar panels.[36] Self-healing materials, polymers and composite materials capable of mending cracks have been produced based on biological materials.[37]

The Bombardier beetle's powerful repellent spray inspired a Swedish company to develop a "micro mist" spray technology, which is claimed to have a low carbon impact (compared to aerosol sprays). The beetle mixes chemicals and releases its spray via a steerable nozzle at the end of its abdomen, stinging and confusing the victim.[38]

Most viruses have an outer capsule 20 to 300 nm in diameter. Virus capsules are remarkably robust and capable of withstanding temperatures as high as 60 °C; they are stable across the pH range 2-10.[13] Viral capsules can be used to create nano device components such as nanowires, nanotubes, and quantum dots. Tubular virus particles such as the tobacco mosaic virus (TMV) can be used as templates to create nanofibers and nanotubes, since both the inner and outer layers of the virus are charged surfaces which can induce nucleation of crystal growth. This was demonstrated through the production of platinum and gold nanotubes using TMV as a template.[39] Mineralized virus particles have been shown to withstand various pH values by mineralizing the viruses with different materials such as silicon, PbS, and CdS and could therefore serve as a useful carriers of material.[40] A spherical plant virus called cowpea chlorotic mottle virus (CCMV) has interesting expanding properties when exposed to environments of pH higher than 6.5. Above this pH, 60 independent pores with diameters about 2 nm begin to exchange substance with the environment. The structural transition of the viral capsid can be utilized in Biomorphic mineralization for selective uptake and deposition of minerals by controlling the solution pH. Possible applications include using the viral cage to produce uniformly shaped and sized quantum dot semiconductor nanoparticles through a series of pH washes. This is an alternative to the apoferritin cage technique currently used to synthesize uniform CdSe nanoparticles.[41] Such materials could also be used for targeted drug delivery since particles release contents upon exposure to specific pH levels.

Surface tension biomimetics are being researched for technologies such as hydrophobic or hydrophilic coatings and microactuators.[42][43][44][45][46]

Biomimetic materials are gaining increasing attention in the field of optics and photonics. For example, the chiral self-assembly of cellulose inspired by the Pollia condensata berry has been exploited to make optically active films.[47] Similarly, phase-separation has been used to fabricate ultra-white scattering membranes from polymethylmethacrylate, mimicking the extraordinary properties of the beetle Cyphochilus.

Artificial enzyme

From Wikipedia, the free encyclopedia

Schematic drawing of artificial phosphorylase

An artificial enzyme is a synthetic, organic molecule or ion that recreate some function of an enzyme. The area promises to deliver catalysis at rates and selectivity observed in many enzymes.

History

Enzyme catalysis of chemical reactions occur with high selectivity and rate. The substrate is activated in a small part of the enzyme's macromolecule called the active site. There, the binding of a substrate close to functional groups in the enzyme causes catalysis by so-called proximity effects. It is possible to create similar catalysts from small molecule by combining substrate-binding with catalytic functional groups. Classically artificial enzymes bind substrates using receptors such as cyclodextrin, crown ethers, and calixarene.[1][2]

Artificial enzymes based on amino acids or peptides as characteristic molecular moieties have expanded the field of artificial enzymes or enzyme mimics. For instance, scaffolded histidine residues mimics certain metalloproteins and -enzymes such as hemocyanin, tyrosinase, and catechol oxidase).[3]

Artificial enzymes have been designed from scratch via a computational strategy using Rosetta.[4] In December 2014, it was announced that active enzymes had been produced that were made from artificial molecules which do not occur anywhere in nature.[5] In 2017, a book chapter entitled "Artificial Enzymes: The Next Wave" was published.[1]

Nanozymes

Nanozymes are nanomaterials with enzyme-like characteristics.[6] They have been widely explored for various applications, such as biosensing, bioimaging, tumor diagnosis and therapy, antibiofouling.

1990s

In 1996 and 1997, Dugan et al. discovered the superoxide dismutase (SOD) mimicking activities of fullerene derivatives.[12][13]

2000s

In 2004, the term "nanozymes" was coined by Flavio Manea, Florence Bodar Houillon, Lucia Pasquato, and Paolo Scrimin.[14] In 2006, nanoceria (i.e., CeO2 nanoparticles) was used for preventing retinal degeneration induced by intracellular peroxides.[15][16] In 2007, Xiyun Yan and coworkers reported that ferromagnetic nanoparticles possessed intrinsic peroxidase-like activity.[17][18] In 2008, Hui Wei and Erkang Wang developed an iron oxide nanozyme based sensing platform for bioactive molecules (such as hydrogen peroxide and glucose).[19]

2010s

In 2012, recombinant human heavy-chain ferritin coated iron oxide nanoparticle with peroxidase-like activity was prepared and used for targeting and visualizing tumour tissues.[20] In 2012, vanadium pentoxide nanoparticles with vanadium haloperoxidase mimicking activities were used for preventing marine biofouling.[21] In 2014, it was demonstrated that carboxyfullerene could be used to treat neuroprotection postinjury in Parkinsonian nonhuman primates.[22] In 2015, a supramolecular regulation strategy was proposed to modulate the activity of gold-based nanozymes for imaging and therapeutic applications.[23][24] A nanozyme-strip for rapid local diagnosis of Ebola was developed.[25][26] Nanoceria nanozymes were used for DNA sensing.[27] An integrated nanozyme has been developed for real time monitoring the dynamic changes of cerebral glucose in living brains.[28][29] Cu(OH)2 nanozymes with peroxidase-like activities were reported.[30] Ionic FePt, Fe3O4, Pd, and CdSe NPs with peroxidase-like activities were reported.[31] A book entitled "Nanozymes: Next Wave of Artificial Enzymes" was published.[32] A book chapter entitled "Nanozymes" in the book of "Enzyme Engineering" was published (in Chinese).[33] Oxidase-like nanoceria has been used for developing self-regulated bioassays.[34] Multi-enzyme mimicking Prussian blue was developed for therapeutics.[35] Histidine was used to modulate iron oxide nanoparticles' peroxidase mimicking activities.[36] Gold nanoparticles' peroxidase mimicking activities were modulated via a supramolecular strategy for cascade reactions.[37] A molecular imprinting strategy was developed to improve the selectivity of Fe3O4 nanozymes with peroxidase-like activity.[38] A new strategy was developed to enhance the peroxidase mimicking activity of gold nanoparticles by using hot electrons.[39] Researchers have designed gold nanoparticles (AuNPs) based integrative nanozymes with both SERS and peroxidase mimicking activities for measuring glucose and lactate in living tissues.[40] Cytochrome c oxidase mimicking activity of Cu2O nanoparticles was modulated by receiving electrons from cytochrome c.[41] Fe3O4 NPs were combined with glucose oxidase for tumor therapeutics.[42] Manganese dioxide nanozymes have been used as cytoprotective shells.[43] Mn3O4 Nanozyme for Parkinson's Disease (cellular model) was reported.[44] Heparin elimination in live rats has been monitored with 2D MOF based peroxidase mimics and AG73 peptide.[45] Glucose oxidase and iron oxide nanozymes were encapsulated within multi-compartmental hydrogels for incompatible tandem reactions.[46] A cascade nanozyme biosensor was developed for detection of viable Enterobacter sakazakii.[47] An integrated nanozyme of GOx@ZIF-8(NiPd) was developed for tandem catalysis.[48] Charge-switchable nanozymes were developed.[49] Site-selective RNA splicing nanozyme was developed.[50] A nanozymes special issue in Progress in Biochemistry and Biophysics was published.[51] Mn3O4 nanozymes with ROS scavenging activities have been developed for in vivo anti-inflammation.[52] A concept entitled "A Step into the Future – Applications of Nanoparticle Enzyme Mimics" was proposed.[53] Facet-dependent oxidase and peroxidase-like activities of Pd nanoparticles were reported.[54] Au@Pt multibranched nanostructures as bifunctional nanozymes were developed.[55] Ferritin coated carbon nanozymes were developed for tumor catalytic therapy.[56] CuO nanozymes were developed to kill bacteria via a light-controlled manner.[57] Enzymatic activity of oxygenated CNT was studied.[58] Nanozymes were used to catalyze the oxidation of l-Tyrosine and l-Phenylalanine to dopachrome.[59] Nanozyme as an emerging alternative to natural enzyme for biosensing and immunoassay was summarized.[60]

Conferences

Several conferences have focused on nanozymes. In 2015, a nanozyme workshop for was held at the 9th Asian Biophysics Associatation (ABA) Symposium.[61] In Pittcon 2016, a Networking entitled "Nanozymes in Analytical Chemistry and Beyond" was devoted to nanozymes.[62] An Xiangshan Science Conference was devoted to nanozyme research.[63][64] A scientific session was devoted to "Biomimetic Nanocatalysis" in 15th Chinese Biophysics Congress.[65] The "Nanozymes for Bioanalysis (Oral)" section was included in the 256th ACS National Meeting (2018 Fall, Boston).[66]

Carbon nanotubes too weak to get a space elevator off the ground

carbon nanotubes
Andrey Prokhorov/Getty
For want of an atom, the space elevator failed.

Carbon nanotubes (CNTs) are famed for being a future wonder material that will enable a swathe of super-strong but light applications from racing bikes to computer components.

But now it seems a single out-of-place atom is enough to cut their strength by more than half. That means one of the more outlandish applications for CNT fibres – a sci-fi space elevator – might never happen.

The tubes’ strength is a result of their atomic structure, with walls made from just a single layer of carbon atoms locked in a hexagonal grid. Theoretical studies suggest that a single CNT can have a tensile strength of 100 gigapascals (GPa), making it one of the strongest materials around, but efforts to spin multiple nanotubes into a practical large-scale fibre have only produced ropes with strengths of 1 GPa.

To find out why, Feng Ding of the Hong Kong Polytechnic University and his colleagues simulated CNTs with a single atom out of place, turning two of the hexagons into a pentagon and heptagon, and creating a kink in the tube. They found this simple change was enough to cut the ideal strength of a CNT to 40 GPa, with the effect being even more severe when they increased the number of misaligned atoms.

Fracture sequence

The team’s simulations show that the kink acts as a weak point in the tube, easily snapping the normally strong carbon-carbon bonds. Once this happens, the bonds in the adjacent hexagons also break, unzipping the entire tube. The effect on CNTs spun together into fibres is similar – once one CNT breaks, the strain on the others increases, fracturing them in sequence.

The results suggest just one misplaced atom is enough to weaken an entire CNT fibre, and since nanotube manufacturing processes are flawed at the moment, you will inevitably end up with a bad tube in your fibre.

“Only CNTs with extreme quality are able to retain their ideal strength,” says Ding. “Most mass-produced CNTs are highly defective, and high-quality CNTs are hard to produce in large quantity.”

That’s bad news for people who want to build a space elevator, a cable between the Earth and an orbiting satellite that would provide easy access to space.

Estimates suggest such a cable would need a tensile strength of 50 GPa, so CNTs were a promising solution, but Ding’s research suggests they won’t work. “Unless great breakthroughs on CNT synthesis can be achieved, using CNTs to build a space elevator would be extremely challenging,” he says.

Journal reference: ACS Nano DOI: 10.1021/acsnano.6b03231

Nanomaterials

From Wikipedia, the free encyclopedia

Nanomaterials describe, in principle, materials of which a single unit is sized (in at least one dimension) between 1 to 1000 nanometres (10−9 meter) but usually is 1 to 100 nm (the usual definition of nanoscale[1]).

Nanomaterials research takes a materials science-based approach to nanotechnology, leveraging advances in materials metrology and synthesis which have been developed in support of microfabrication research. Materials with structure at the nanoscale often have unique optical, electronic, or mechanical properties.[2]

Nanomaterials are slowly becoming commercialized[3] and beginning to emerge as commodities.[4]

Definition

There are significant differences among agencies on the definition of a nanomaterial.[5]

In ISO/TS 80004, nanomaterial is defined as a "material with any external dimension in the nanoscale or having internal structure or surface structure in the nanoscale", with nanoscale defined as the "length range approximately from 1 nm to 100 nm". This includes both nano-objects, which are discrete pieces of material, and nanostructured materials, which have internal or surface structure on the nanoscale; a nanomaterial may be a member of both these categories.[6]

On 18 October 2011, the European Commission adopted the following definition of a nanomaterial: "A natural, incidental or manufactured material containing particles, in an unbound state or as an aggregate or as an agglomerate and for 50% or more of the particles in the number size distribution, one or more external dimensions is in the size range 1 nm – 100 nm. In specific cases and where warranted by concerns for the environment, health, safety or competitiveness the number size distribution threshold of 50% may be replaced by a threshold between 1% to 50%."[7]

Sources

Engineered

Engineered nanomaterials have been deliberately engineered and manufactured by humans to have certain required properties.[8]

Legacy nanomaterials are those that were in commercial production prior to the development of nanotechnology as incremental advancements over other colloidal or particulate materials.[9][10][11] They include carbon black and titanium dioxide nanoparticles.[12]

Incidental

Nanomaterials may be incidentally produced as a byproduct of mechanical or industrial processes.Sources of incidental nanoparticles include vehicle engine exhausts, welding fumes, combustion processes from domestic solid fuel heating and cooking. Incidental atmospheric nanoparticles are often referred to as ultrafine particles, and are a contributor to air pollution.[13]

Natural

Biological systems often feature natural, functional nanomaterials. The structure of foraminifera (mainly chalk) and viruses (protein, capsid), the wax crystals covering a lotus or nasturtium leaf, spider and spider-mite silk,[14] the blue hue of tarantulas,[15] the "spatulae" on the bottom of gecko feet, some butterfly wing scales, natural colloids (milk, blood), horny materials (skin, claws, beaks, feathers, horns, hair), paper, cotton, nacre, corals, and even our own bone matrix are all natural organic nanomaterials.

Natural inorganic nanomaterials occur through crystal growth in the diverse chemical conditions of the Earth's crust. For example, clays display complex nanostructures due to anisotropy of their underlying crystal structure, and volcanic activity can give rise to opals, which are an instance of a naturally occurring photonic crystals due to their nanoscale structure. Fires represent particularly complex reactions and can produce pigments, cement, fumed silica etc.

Natural sources of nanoparticles include combustion products forest fires, volcanic ash, ocean spray, and the radioactive decay of radon gas. Natural nanomaterials can also be formed through weathering processes of metal- or anion-containing rocks, as well as at acid mine drainage sites.[13]
Gallery of natural nanomaterials

Types

Nano-objects are often categorized as to how many of their dimensions fall in the nanoscale. A nanoparticle is defined a nano-object with all three external dimensions in the nanoscale, whose longest and the shortest axes do not differ significantly. A nanofiber has two external dimensions in the nanoscale, with nanotubes being hollow nanofibers and nanorods being solid nanofibers. A nanoplate has one external dimension in the nanoscale, and if the two larger dimensions are significantly different it is called a nanoribbon. For nanofibers and nanoplates, the other dimensions may or may not be in the nanoscale, but must be significantly larger. A significant different in all cases is noted to be typically at least a factor of 3.[16]

Nanostructured materials are often categorized by what phases of matter the contain. A nanocomposite is a solid containing at least one physically or chemically distinct region, or collection of regions, having at least one dimension in the nanoscale.. A nanofoam has a liquid or solid matrix, filled with a gaseous phase, where either phase has dimensions on the nanoscale. A nanoporous material is a solid material containing nanopores, cavities with dimensions on the nanoscale. A nanocrystalline material has a significant fraction of crystal grains in the nanoscale.[17]

The above definitions are all according to ISO/TS 80004. In other sources, nanoporous materials and nanofoam are sometimes considered nanostructures but not nanomaterials because only the voids and not the materials themselves are nanoscale.[18] Although the ISO definition only considers round nano-objects to be nanoparticles, other sources use the term nanoparticle for all shapes.[19]

Nanoparticles

Nanoparticles have all three dimensions on the nanoscale. Nanoparticles can also be embedded in a bulk solid to form a nanocomposite.[18]

Fullerenes

The fullerenes are a class of allotropes of carbon which conceptually are graphene sheets rolled into tubes or spheres. These include the carbon nanotubes (or silicon nanotubes) which are of interest both because of their mechanical strength and also because of their electrical properties.[20]

Rotating view of C60, one kind of fullerene.

The first fullerene molecule to be discovered, and the family's namesake, buckminsterfullerene (C60), was prepared in 1985 by Richard Smalley, Robert Curl, James Heath, Sean O'Brien, and Harold Kroto at Rice University. The name was a homage to Buckminster Fuller, whose geodesic domes it resembles. Fullerenes have since been found to occur in nature.[21] More recently, fullerenes have been detected in outer space.[22]

For the past decade, the chemical and physical properties of fullerenes have been a hot topic in the field of research and development, and are likely to continue to be for a long time. In April 2003, fullerenes were under study for potential medicinal use: binding specific antibiotics to the structure of resistant bacteria and even target certain types of cancer cells such as melanoma. The October 2005 issue of Chemistry and Biology contains an article describing the use of fullerenes as light-activated antimicrobial agents. In the field of nanotechnology, heat resistance and superconductivity are among the properties attracting intense research.

A common method used to produce fullerenes is to send a large current between two nearby graphite electrodes in an inert atmosphere. The resulting carbon plasma arc between the electrodes cools into sooty residue from which many fullerenes can be isolated.

There are many calculations that have been done using ab-initio Quantum Methods applied to fullerenes. By DFT and TDDFT methods one can obtain IR, Raman and UV spectra. Results of such calculations can be compared with experimental results.

Metal-based nanoparticles

Inorganic nanomaterials, (e.g. quantum dots, nanowires and nanorods) because of their interesting optical and electrical properties, could be used in optoelectronics.[23] Furthermore, the optical and electronic properties of nanomaterials which depend on their size and shape can be tuned via synthetic techniques. There are the possibilities to use those materials in organic material based optoelectronic devices such as Organic solar cells, OLEDs etc. The operating principles of such devices are governed by photoinduced processes like electron transfer and energy transfer. The performance of the devices depends on the efficiency of the photoinduced process responsible for their functioning. Therefore, better understanding of those photoinduced processes in organic/inorganic nanomaterial composite systems is necessary in order to use them in optoelectronic devices.

Nanoparticles or nanocrystals made of metals, semiconductors, or oxides are of particular interest for their mechanical, electrical, magnetic, optical, chemical and other properties.[24][25] Nanoparticles have been used as quantum dots and as chemical catalysts such as nanomaterial-based catalysts. Recently, a range of nanoparticles are extensively investigated for biomedical applications including tissue engineering, drug delivery, biosensor.[26] [27]

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 this is often not the case. Size-dependent properties are observed such as quantum confinement in semiconductor particles, surface plasmon resonance in some metal particles and superparamagnetism in magnetic materials.

Nanoparticles exhibit a number of special properties relative to bulk material. For example, the bending of bulk copper (wire, ribbon, etc.) occurs with movement of copper atoms/clusters at about the 50 nm scale. Copper nanoparticles smaller than 50 nm are considered super hard materials that do not exhibit the same malleability and ductility as bulk copper. The change in properties is not always desirable. Ferroelectric materials smaller than 10 nm can switch their magnetisation direction using room temperature thermal energy, thus making them useless for memory storage. Suspensions of nanoparticles are possible because the interaction of the particle surface with the solvent is strong enough to overcome differences in density, which usually result in a material either sinking or floating in a liquid. Nanoparticles often have unexpected visual properties because they are small enough to confine their electrons and produce quantum effects. For example, gold nanoparticles appear deep red to black in solution.

The often very high surface area to volume ratio of nanoparticles provides a tremendous driving force for diffusion, especially at elevated temperatures. Sintering is possible at lower temperatures and over shorter durations than for larger particles. This theoretically does not affect the density of the final product, though flow difficulties and the tendency of nanoparticles to agglomerate do complicate matters. The surface effects of nanoparticles also reduces the incipient melting temperature.

One-dimensional nanostructures

The smallest possible crystalline wires with cross-section as small as a single atom can be engineered in cylindrical confinement [28][29][30]. Carbon nanotubes, a natural semi-1D nanostructure, can be used as a template for synthesis. Confinement provides mechanical stabilization and prevents linear atomic chains from disintegration; other structures of 1D nanowires are predicted to be mechanically stable even upon isolation from the templates [31][32].

Two-dimensional nanostructures

2D materials are crystalline materials consisting of a two-dimensional single layer of atoms. The most important representative graphene was discovered in 2004.

Box-shaped graphene (BSG) nanostructure is an example of 3D nanomaterial.[33] BSG nanostructure has appeared after mechanical cleavage of pyrolytic graphite. This nanostructure is a multilayer system of parallel hollow nanochannels located along the surface and having quadrangular cross-section. The thickness of the channel walls is approximately equal to 1 nm. The typical width of channel facets makes about 25 nm.

Thin films with nanoscale thicknesses are considered nanostructures, but are sometimes not considered nanomaterials because they do not exist separately from the substrate.[18]

Bulk nanostructured materials

Some bulk materials contain features on the nanoscale, including nanocomposites, nanocrystalline materials, nanostructured films, and nanotextured surfaces.[18]

Applications

Nano materials are used in a variety of, manufacturing processes, products and healthcare including paints, filters, insulation and lubricant additives. In healthcare Nanozymes are nanomaterials with enzyme-like characteristics.[34] They are an emerging type of artificial enzyme, which have been used for wide applications in such as biosensing, bioimaging, tumor diagnosis,[35] antibiofouling and more. In paints nanomaterials are used to improve UV protection and improve ease of cleaning.[36] High quality filters may be produced using nanostructures, these filters are capable of removing particulate as small as a virus as seen in a water filter created by Seldon Technologies. In the air purification field, nano technology was used to combat the spread of MERS in Saudi Arabian hospitals in 2012.[37] Nanomaterials are being used in modern and human-safe insulation technologies, in the past they were found in Asbestos-based insulation.[38] As a lubricant additive, nano materials have the ability to reduce friction in moving parts. Worn and corroded parts can also be repaired with self-assembling anisotropic nanoparticles called TriboTEX.[37]

Synthesis

The goal of any synthetic method for nanomaterials is to yield a material that exhibits properties that are a result of their characteristic length scale being in the nanometer range (1 – 100 nm).

Accordingly, the synthetic method should exhibit control of size in this range so that one property or another can be attained. Often the methods are divided into two main types "Bottom Up" and "Top Down."

Bottom up methods

Bottom up methods involve the assembly of atoms or molecules into nanostructured arrays. In these methods the raw material sources can be in the form of gases, liquids or solids. The latter requiring some sort of disassembly prior to their incorporation onto a nanostructure. Bottom methods generally fall into two categories: chaotic and controlled.

Chaotic processes involve elevating the constituent atoms or molecules to a chaotic state and then suddenly changing the conditions so as to make that state unstable. Through the clever manipulation of any number of parameters, products form largely as a result of the insuring kinetics. The collapse from the chaotic state can be difficult or impossible to control and so ensemble statistics often govern the resulting size distribution and average size. Accordingly, nanoparticle formation is controlled through manipulation of the end state of the products. Examples of Chaotic Processes are: Laser ablation, Exploding wire, Arc, Flame pyrolysis, Combustion, Precipitation synthesis techniques.

Controlled Processes involve the controlled delivery of the constituent atoms or molecules to the site(s) of nanoparticle formation such that the nanoparticle can grow to a prescribed sizes in a controlled manner. Generally the state of the constituent atoms or molecules are never far from that needed for nanoparticle formation. Accordingly, nanoparticle formation is controlled through the control of the state of the reactants. Examples of controlled processes are self-limiting growth solution, self-limited chemical vapor deposition, shaped pulse femtosecond laser techniques, and molecular beam epitaxy.

Characterization

Novel effects can occur in materials when structures are formed with sizes comparable to any one of many possible length scales, such as the de Broglie wavelength of electrons, or the optical wavelengths of high energy photons. In these cases quantum mechanical effects can dominate material properties. One example is quantum confinement where the electronic properties of solids are altered with great reductions in particle size. The optical properties of nanoparticles, e.g. fluorescence, also become a function of the particle diameter. This effect does not come into play by going from macrosocopic to micrometer dimensions, but becomes pronounced when the nanometer scale is reached.
In addition to optical and electronic properties, the novel mechanical properties of many nanomaterials is the subject of nanomechanics research. When added to a bulk material, nanoparticles can strongly influence the mechanical properties of the material, such as the stiffness or elasticity. For example, traditional polymers can be reinforced by nanoparticles (such as carbon nanotubes) resulting in novel materials which can be used as lightweight replacements for metals. Such composite materials may enable a weight reduction accompanied by an increase in stability and improved functionality.[39]

Finally, nanostructured materials with small particle size such as zeolites, and asbestos, are used as catalysts in a wide range of critical industrial chemical reactions. The further development of such catalysts can form the basis of more efficient, environmentally friendly chemical processes.

The first observations and size measurements of nano-particles were made during the first decade of the 20th century. Zsigmondy made detailed studies of gold sols and other nanomaterials with sizes down to 10 nm and less. He published a book in 1914.[40] He used an ultramicroscope that employs a dark field method for seeing particles with sizes much less than light wavelength.

There are traditional techniques developed during 20th century in Interface and Colloid Science for characterizing nanomaterials. These are widely used for first generation passive nanomaterials specified in the next section.

These methods include several different techniques for characterizing particle size distribution. This characterization is imperative because many materials that are expected to be nano-sized are actually aggregated in solutions. Some of methods are based on light scattering. Others apply ultrasound, such as ultrasound attenuation spectroscopy for testing concentrated nano-dispersions and microemulsions.[41]

There is also a group of traditional techniques for characterizing surface charge or zeta potential of nano-particles in solutions. This information is required for proper system stabilzation, preventing its aggregation or flocculation. These methods include microelectrophoresis, electrophoretic light scattering and electroacoustics. The last one, for instance colloid vibration current method is suitable for characterizing concentrated systems.

Uniformity

The chemical processing and synthesis of high performance technological components for the private, industrial and military sectors requires the use of high purity ceramics, polymers, glass-ceramics and material composites. In condensed bodies formed from fine powders, the irregular sizes and shapes of nanoparticles in a typical powder often lead to non-uniform packing morphologies that result in packing density variations in the powder compact.

Uncontrolled agglomeration of powders due to attractive van der Waals forces can also give rise to in microstructural inhomogeneities. Differential stresses that develop as a result of non-uniform drying shrinkage are directly related to the rate at which the solvent can be removed, and thus highly dependent upon the distribution of porosity. Such stresses have been associated with a plastic-to-brittle transition in consolidated bodies, and can yield to crack propagation in the unfired body if not relieved.[42][43] [44]

In addition, any fluctuations in packing density in the compact as it is prepared for the kiln are often amplified during the sintering process, yielding inhomogeneous densification. Some pores and other structural defects associated with density variations have been shown to play a detrimental role in the sintering process by growing and thus limiting end-point densities. Differential stresses arising from inhomogeneous densification have also been shown to result in the propagation of internal cracks, thus becoming the strength-controlling flaws. [45][46]

It would therefore appear 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 particle-particle interactions. It should be noted here that a number of dispersants such as ammonium citrate (aqueous) and imidazoline or oleyl alcohol (nonaqueous) are promising solutions as possible additives for enhanced dispersion and deagglomeration. Monodisperse nanoparticles and colloids provide this potential.[47]

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. The degree of order appears to be limited by the time and space allowed for longer-range correlations to be established. Such defective polycrystalline colloidal structures would appear to be the basic elements of sub-micrometer colloidal materials science, and, therefore, provide the first step in developing a more rigorous understanding of the mechanisms involved in microstructural evolution in high performance materials and components.

Health and safety

World Health Organization guidelines

The World Health Organization (WHO) published a guideline on protecting workers from potential risk of manufactured nanomaterials at the end of 2017.[50] WHO used a precautionary approach as one of its guiding principles. This means that exposure has to be reduced, despite uncertainty about the adverse health effects, when there are reasonable indications to do so. In addition, the hierarchy of controls was an important guiding principle. This means that when there is a choice between control measures, those measures that are closer to the root of the problem should always be preferred over measures that put a greater burden on workers, such as the use of personal protective equipment (PPE). WHO commissioned systematic reviews for all important issues to assess the current state of the science and to inform the recommendations according to the process set out in the WHO Handbook for guideline development. The recommendations were rated as “strong” or “conditional” depending on the quality of the scientific evidence, values and preferences, and costs related to the recommendation.

The WHO guidelines contain the following recommendations for safe handling of MNMs:

A. Assess health hazards of MNMs
  1. WHO recommends assigning hazard classes to all MNMs according to the Globally Harmonized System (GHS) of Classification and Labelling of Chemicals for use in safety data sheets. For a limited number of MNMs this information is made available in the guidelines (strong recommendation, moderate-quality evidence).
  2. WHO recommends updating safety data sheets with MNM-specific hazard information or indicating which toxicological end-points did not have adequate testing available (strong recommendation, moderate-quality evidence).
  3. For the respirable fibres and granular biopersistent particles’ groups, the GDG suggests using the available classification of MNMs for provisional classification of nanomaterials of the same group (conditional recommendation, low-quality evidence).
B. Assess exposure to MNMs
  1. WHO suggests assessing workers’ exposure in workplaces with methods similar to those used for the proposed specific occupational exposure limit (OEL) value of the MNM (conditional recommendation, low-quality evidence).
  2. Because there are no specific regulatory OEL values for MNMs in workplaces, WHO suggests assessing whether workplace exposure exceeds a proposed OEL value for the MNM. A list of proposed OEL values is provided in an annex of the guidelines. The chosen OEL should be at least as protective as a legally mandated OEL for the bulk form of the material (conditional recommendation, low-quality evidence).
  3. If specific OELs for MNMs are not available in workplaces, WHO suggests a step-wise approach for inhalation exposure with, first an assessment of the potential for exposure; second, conducting basic exposure assessment and third, conducting a comprehensive exposure assessment such as those proposed by the Organisation for Economic Cooperation and Development (OECD) or Comité Européen de Normalisation (the European Committee for Standardization, CEN) (conditional recommendation, moderate quality evidence).
  4. For dermal exposure assessment, WHO found that there was insufficient evidence to recommend one method of dermal exposure assessment over another.
C. Control exposure to MNMs
  1. Based on a precautionary approach, WHO recommends focusing control of exposure on preventing inhalation exposure with the aim of reducing it as much as possible (strong recommendation, moderate-quality evidence).
  2. WHO recommends reduction of exposures to a range of MNMs that have been consistently measured in workplaces especially during cleaning and maintenance, collecting material from reaction vessels and feeding MNMs into the production process. In the absence of toxicological information, WHO recommends implementing the highest level of controls to prevent workers from any exposure. When more information is available, WHO recommends taking a more tailored approach (strong recommendation, moderate-quality evidence).
  3. WHO recommends taking control measures based on the principle of hierarchy of controls, meaning that the first control measure should be to eliminate the source of exposure before implementing control measures that are more dependent on worker involvement, with PPE being used only as a last resort. According to this principle, engineering controls should be used when there is a high level of inhalation exposure or when there is no, or very little, toxicological information available. In the absence of appropriate engineering controls PPE should be used, especially respiratory protection, as part of a respiratory protection programme that includes fit-testing (strong recommendation, moderate-quality evidence).
  4. WHO suggests preventing dermal exposure by occupational hygiene measures such as surface cleaning, and the use of appropriate gloves (conditional recommendation, low quality evidence).
  5. When assessment and measurement by a workplace safety expert is not available, WHO suggests using control banding for nanomaterials to select exposure control measures in the workplace. Owing to a lack of studies, WHO cannot recommend one method of control banding over another (conditional recommendation, very low-quality evidence).
For health surveillance WHO could not make a recommendation for targeted MNM-specific health surveillance programmes over existing health surveillance programmes that are already in use owing to the lack of evidence. WHO considers training of workers and worker involvement in health and safety issues to be best practice but could not recommend one form of training of workers over another, or one form of worker involvement over another, owing to the lack of studies available. It is expected that there will be considerable progress in validated measurement methods and risk assessment and WHO expects to update these guidelines in five years’ time, in 2022.

Other guidance

Because nanotechnology is a recent development, the health and safety effects of exposures to nanomaterials, and what levels of exposure may be acceptable, are subjects of ongoing research.[8] Of the possible hazards, inhalation exposure appears to present the most concern. Animal studies indicate that carbon nanotubes and carbon nanofibers can cause pulmonary effects including inflammation, granulomas, and pulmonary fibrosis, which were of similar or greater potency when compared with other known fibrogenic materials such as silica, asbestos, and ultrafine carbon black. Although the extent to which animal data may predict clinically significant lung effects in workers is not known, the toxicity seen in the short-term animal studies indicate a need for protective action for workers exposed to these nanomaterials, although no reports of actual adverse health effects in workers using or producing these nanomaterials were known as of 2013.[51] Additional concerns include skin contact and ingestion exposure,[51][52][53] and dust explosion hazards.[54][55]

Elimination and substitution are the most desirable approaches to hazard control. While the nanomaterials themselves often cannot be eliminated or substituted with conventional materials,[8] it may be possible to choose properties of the nanoparticle such as size, shape, functionalization, surface charge, solubility, agglomeration, and aggregation state to improve their toxicological properties while retaining the desired functionality.[56] Handling procedures can also be improved, for example, using a nanomaterial slurry or suspension in a liquid solvent instead of a dry powder will reduce dust exposure.[8] Engineering controls are physical changes to the workplace that isolate workers from hazards, mainly ventilation systems such as fume hoods, gloveboxes, biosafety cabinets, and vented balance enclosures.[57] Administrative controls are changes to workers' behavior to mitigate a hazard, including training on best practices for safe handling, storage, and disposal of nanomaterials, proper awareness of hazards through labeling and warning signage, and encouraging a general safety culture. Personal protective equipment must be worn on the worker's body and is the least desirable option for controlling hazards.[8] Personal protective equipment normally used for typical chemicals are also appropriate for nanomaterials, including long pants, long-sleeve shirts, and closed-toed shoes, and the use of safety gloves, goggles, and impervious laboratory coats.[57] In some circumstances respirators may be used.[56]

Exposure assessment is a set of methods used to monitor contaminant release and exposures to workers. These methods include personal sampling, where samplers are located in the personal breathing zone of the worker, often attached to a shirt collar to be as close to the nose and mouth as possible; and area/background sampling, where they are placed at static locations. The assessment should use both particle counters, which monitor the real-time quantity of nanomaterials and other background particles; and filter-based samples, which can be used to identify the nanomaterial, usually using electron microscopy and elemental analysis.[56][58] As of 2016, quantitative occupational exposure limits have not been determined for most nanomaterials. The U.S. National Institute for Occupational Safety and Health has determined non-regulatory recommended exposure limits for carbon nanotubes, carbon nanofibers,[51] and ultrafine titanium dioxide.[59] Agencies and organizations from other countries, including the British Standards Institute[60] and the Institute for Occupational Safety and Health in Germany,[61] have established OELs for some nanomaterials, and some companies have supplied OELs for their products.[8]

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