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Physical (Emergent) Properties

Between the dimensions on an atomic scale and bulk scale, there is a size range where matter exhibits some speci c
properties which may be remarkably di erent from the physical and chemical (physico chemical) properties of bulk
materials. In context of nanotechnology, these are referred to as "Emergent Properties". Some of these peculiar
properties are known but many may yet be discovered. Many applications of nano-technology are based on utilizing
these properties. Hence its important to consider them for strengthening the case of characterizing nano-particles as
"new materials".

Emergent Properties related to nanotoxicity

Emergent properties and their role in nanoparticle (NP) toxicity has been studied in recent research which concluded in
relating it to their physical and chemical properties.
From the earlier experience of toxicological properties of brous particles (such as asbestos), it was expected that the
most critical parameters in determining adverse health e ects of nanoparticles will be dose, dimension and
durability[1]. However, recent studies have indicated relation between several physicochemical properties of
nanoparticles and their associated health e ects, raising some uncertainties in determining the most important factors
in deciding their toxicity: mass, number, size, bulk or surface chemistry, aggregation, or all combined. The following
explains which are the most important nanoparticle characteristics associated with their toxicity.

Large surface to volume ratio

Extreme reactivity
Aggregation
Di erent particle chemistry and crystalline structure
Aspect-ratio
Surface coating and functionalization

Though these properties can be linked to nanotoxicity, there remain several other properties which are evident at
nanoscale. They indicate that these nanoparticle needs special and di erent treatment than their bulk materials. Some
of the known physical properties of nanoparticles are related to di erent origin such as; (i) large fraction of surface
atoms, (ii) large surface energy, (iii) spatial con nement, and (iv) reduced imperfection. Some of the resultant
properties due to these features are:

Thermodynamics -Signi cantly lower melting point or phase transition temperature

Enhanced mechanical strength due to reduced probability in crystal defects
Di erent optical property
Di erence in electrical conductivity
Transfer of Ferromagnetism to Supermagnetism at nano scale
Self-puri cation

Surface area (and not dose) in uencing toxicity:

Dose is de ned a the amount or quantity of substance that will reach a biological system. The dose is directly related to
exposure or the concentration of substance in the relevant medium (air, food and water) multiplied be the duration of
contact.
Generally, negative health of nanoparticles do no correlate with increase in there mass dosage [2],[3],[4] (see Fig. 1) .
Upon comparing the e ects of inhaled TiO2 nanoparticles with di erent sizes, it was noted that low dose (10 mg/m3)
exposure to 20 nm diameter particles resulted in a greater lung tumor incidence than the high dose (250 mg/m3) of
300 nm diameter particles [5](1.30). Hence, the e ect that plays the role here is surface area and not the mass dose
(Fig. 1)[6].

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(../../../imx/Surface_toxicity.jpg)

Figure 1 (a). Inflammation generated by instillation of low-toxicity particles (carbon black, titanium dioxide and
polystyrene) with the dose expressed as surface area . (b).Indication of oxidation induced fluorescence for
nanoparticles and microparticles versus mass dose.

Since for the same mass of particles with the same chemical composition and crystalline structure, a greater toxicity
was found from the nanoparticles than their larger counterparts. This suggested that the in ammatory e ect may be
dependent on the surface area of nanoparticles; therefore, this calls for change in de nitions and regulations related
to dose and exposure limits. For the same mass concentrations, smaller particles have greater number of particles and
greater surface area. Larger surface area leads to increased reactivity [7] and in increased source of reactive oxygen
species, oxidation [8]and DNA damage as demonstrated by in vitro experiments[9].

A simple calculation to evaluate risk:

Studies suggested a threshold of 20 cm2 surface area of instilled nanoparticles below which there is no in ammatory
response in mice. Extrapolating this to humans, the critical surface area of nanoparticles becomes 30,000 cm2. In a
busy urban area with nanoparticle concentrations upto 10 µg/m3, with speci c surface area of 100 m2 /g, and the
deposition e ciency of 70%, the lung burden result in 150cm2 per day. If deposited particles accumulate in the lungs,
the surface threshold for signi cant in ammatory e ects is reached in about half a year [10].

Extreme reactivity:
The case study of copper nanoparticles points out the extreme toxicity arising due to high chemical activity resulting
from small size and large surface area.
Copper has been used widely in industry and day to day purposes which indicates that toxicity of microsized copper is
very low. Nano sized copper is used as additive and metallic coating. Recent work has shown that toxicity of copper
nanoparticles is signi cantly di erent from that of copper micron particles in mice[11]. Biological activity of copper
increases with decrease in particle size. The oral 50% lethal dose (LD 50) of 23.5 nm copper particles was 413mg/kg,
making it moderate toxic (Class 3) in Hodge and Sterner Scale, while LD50 of 17.0 µm particles is more than 5000
mg/kg, and it belongs to non-toxic (Class 5). Nanoparticles toxicological a ects associated with kidney, liver and spleen
of experimental mice but micro- copper particles do not, on a mass basis[12].
The nanotoxicity of copper has been partly explained in chain of “ size-chemical reactivity - toxicity”. The smaller size
leads to high chemical reactivity resulting in profound toxicity. After their uptake in alimentary canal, the nano-copper
particles react with hydrochloric acid in gastric juice and are converted into copper ions which are very toxic and have
even lead to mortality of experimental mice in nano-copper treated group[13].
Ultrahigh active nanoparticle easily interacts with local tissues and nearby biological molecules. Figure 2 explains the
phenomenon taking place in stomach when copper particles of di erent sizes enter into the body. Micron sized
particles can generate few ions (2b) whereas abundant copper ons can be transformed from the metallic form in nano
sized copper group(2a)[14].

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(../../../imx/Copper_nanoparticles.jpg#Copper_nanoparticles.jpg] )
Fig. 2. Schematic diagrams show the generation of highly toxic cupric ions in the gastric juice. Nanosized copper
particles lead to a massive generation of cupric ions which are highly toxic in vivo (a), and few cupric ions are generated
with microsized copper particles (b)

Aggregation:
Aggregation of nanoparticles may depend surface charge, material type and size. Aggregation plays an important role
in determining the toxicity of nanoparticles. There is more e ective clearance for larger particles compared to smaller
ones by macrophages. Therefore, aggregates larger than 100-200 nm [15],[16] exhibit reduced toxicity. It has been
shown that a high concentration of nanoparticles will promote particle aggregation, and therefore reduce toxic e ects
compared to lower concentrations. Most aggregates are seen to be larger than 100 nm, a size which serves as
threshold for many adverse e ects of small particles. Therefore, risk evaluation needs to consider concentration factor
which leads to di erence in aggregation, thus resulting in di erence in potential toxicity of nanoparticles.

Particle chemistry and crystalline structure:

Although more concern has been shown over size of nanoparticles than their chemistry in determining toxicity, [17]
generally, results of studies showing similar extent of in ammation by di erent nanoparticle chemistries cannot be
extrapolated. Particle chemistry plays critical role in determining toxicity. Depending on chemistry, particles can show
di erent cellular uptake, sub-cellular localization, and ability to catalyze generation of reactive oxygen species[18].
Composition and chemistry of particles must be distinctly distinguished. It is possible that the particles of same
composition may posses di erent chemical or crystalline structure. Crystalline form also determines the toxicity of a
material. For example, rutile and anatase are allotropes of titanium oxide ( polymorphs with the same chemical
composition, but di erent crystalline structures, and hence, di erent chemical and physical properties). Rutile
nanoparticles (200 nm) have been reported to indue oxidative DNA damage in the absence of light, but anatase
nanoparticles of the same size did not[19].
Nanoparticles often exhibit unexpected crystal structure due to surface e ects.The evaporation condensation study
done in order to synthesize collection of gold micro and nanoparticles describes generation of 25 nm nanoparticles
along-with some larger particles.(1.347) A unique behavior emerges from these and other nanomaterials when small
clusters of atoms form and manifests quantum e ects.

Aspect-ratio
It was found that a higher toxic ratio increases toxicity of a particle. Speci cally, lung cancer, mesothelioma and
asbestosis was found to be associated with asbestos particles longer than 10 µm, 5 µm and 2 µm respectively. All of
these particles had a minimum thickness of 150 µm[20]. Fibers longer than 20 µm (for humans) will not be cleared from
respiratory tract by phagocytosis e ectively. Biopersistence of these long-aspect-ratio bers leads to long term
carcinogenic e ects, as shown in Fig. 3[21].

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(../../../imx/Fiber_health_indices.jpg)

Fiber health indices describing disease associated to bers of di erent size.

Long aspect ratio engineered nanoparticles such as carbon nanotubes (CNTs) have attracted a lot of attention due to
their possible negative health e ects[22],[23],[24],[25],[26],[27],[28],[29],[30]. This is owing to the morphological similarities of
these CNTs with asbestos. Still, there has been no consensus in the characterization of CNT toxicity.

CNT toxicity has also been associated to factors such as morphologies, sizes, chemical functionalizations and their
surface ends[31]. The conclusions on general points that CNTs are very toxic[32],[33]. Long aspect ratio particles were
reported to produce signi cant pulmonary toxicity than spherical ones[34]. Pharyngeal introduction of Single Wall
Carbon Nano Tubes (SWCNTs) resulted in onset of progressive granulomas in rats. Whereas, equal dosage of carbon
black or silica nanoparticles did not induce granulomas, alveolar wall thickening. They caused only weak in ammation
and limited damage. (1.302) The enhanced toxicity was attributed to physicochemical properties and brous nature of
carbon nanotubes.

Surface coating and functionalization

Surface coating and functionalization: Particle surface plays a critical role in toxicity as it interacts with cells and other
biological entities. Surfactants can change the physicochemical properties of nanoparticles such as magnetic, electric,
optical and chemical reactivity[35], which a ects their cytotoxicity. Surface coating can make harmful nanoparticles
nontoxic, while increases toxicity of other harmless particles. The presence of oxygen, ozone , oxygen radicals and
transition metals on nanoparticle surface leads to the creation of reactive oxygen species[36].

Other emergent properties[37],[38]

Melting point

(../../../imx/Gold_melting.jpg)

Fig. 1. Melting temperature of gold particles as a function of characteristic length [39].

Nanoparticles of metals, inert gases, semiconductors and molecular crystals are all found to have lower melting
temperatures than their bulk forms, upon decreasing the particle size below 100 nm. In general, this can be explained
by the fact that surface energy increases with decreasing size. Therefore, phase transition (melting is a kind of phase
transition) temperature follows the same scaling law as the surface area/ volume (SAV) ratio ~1/r (r is the characteristic
dimension: radius of a sphere, side of a cube etc.; see more in Surface properties (Surface_properties.php)).
For example, melting point of bulk gold is 1337K and decreases rapidly for nanoparticles with size below 5 nm as
shown in Fig. 1. Such size dependence has also been found in particles and lms of materials such as copper, tin,
indium, lead and bismuth.

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Phase transitions
The nature of the phase transition itself changes at small scales. It broadens: at the same time signi cant portions of a
nanoscale materials can behave as two distinct phases: liquid and solid, for example. Among particular phenomena
occuring at the nanoscale are negative heat capacities [40]. This means that temperature of a nanoparticle can drop
when it is heated.

Crystal structure
A change of crystal structure may occur when the dimension of materials is su ciently small. For example, Arlt et al.
reported that crystal structure of BaTiO3 changes with particle size at room temperature. Gold, known to have a face-
centered cubic (fcc) crystal structure in bulk, is characterized by di erent geometry (or possibly geometries) at the
nanoscale(evidence exists for icosahedral, decahedral and other crystal lattices) [41].

Mechanical strength

(../../../imx/Stress_strain.png)

Fig.2
Mechanical properties of materials increase with a decreasing size. A lot of work in this regard has been done on
whiskers; and it has been found that increase in mechanical strength starts at the micrometer scale, which is noticeably
di erent from other size dependent properties.
Two possible explanations have been proposed to explain enhanced strength of nanowires and nanorods (with
diameter less than 10 microns). These are: increased strength due to high internal perfection in nanowires; second one
being perfection of side faces resulting in less surface defects.
Experimentally, it has been found that nanostructured metals can have higher as well as lower hardness and strength
compared to coarse grained materials, depending on the method used to vary grain size. Although signi cant work has
been done on silver, copper, palladium, gold, iron and nickel, actual role of grain size on mechanical properties is still
not clear. Other properties such as Youngs modulus, creep and superplasticity have also been studied, however, a
conclusion is yet to be relating these properties to size dependence of particles.
Nanomaterials may have di erent elastoplasticity from that of large grained bulk materials. For example, near perfect
elastoelasticity was observed in pure nanocrystalline copper prepared by powdered metallurgy, as shown in the Fig. 2.

Neither work hardening nor neck formation was observed in tensile tests, which is common characteristics of ductile
metals and alloys.

Quantum e ects

Band gap

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(../../../imx/Band_gap.jpg)

Fig. 3. Evolution of band gap and density of states [40].

Atoms possess well known atomic orbitals: they de ne the state of the atom (distribution of its electrons). Transitions
between the states of a single atom are quantized. Bulk materials are composed of a very large number of atoms in
the states of similar energies - bands. Within a band energy di erence between adjacent energy states is negligibly
small. However, a signi cant energy gap between the bands (band gap) can exist. Depending on its magnitude,
materials are classi ed as metallic (no band gap), insulators (very large - >>kT - band gap) and semiconductors (in
between).
Band gap varies with the size of material, as depicted in Fig. 3. Note also that the number of permitted energy states of
the material per unit energy (so called density of states) also decreases with decreasing size: it's very large in bulk
materials (so that transitions are basically continuous), while at small scale particles behave more like individual atoms.

Optical properties

(../../../imx/Fluorescence_of_CdSe-CdS.jpg)

Fluorescence of CdSe-CdS nanoparticles with a diameter of 1.7 nm (blue) to 6 nm (red) [40]

Above discussion has important implications for the optical properties of nanoparticles. A colorful (in every sense of
the word) example is shown in Fig. 4. It shows uorescing CdSe-CdS nanoparticles. Fluorescence is the emission of light
with a larger wavelength upon absorption. The smaller the particle, the larger the band gap, and, consequently, the
shorter the emitted wavelength.

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(../../../imx/Spr.png)

Fig. 3. Size dependence of absorption spectra of 22, 48 and 99nm spherical gold nanoparticles
Another speci c optical property at the nanoscale is surface plasmon resonance. This refers to a coherent excitation of
all free electron within the conduction band, leading to an in-phase oscillation. When the size of metal nanocrystal is
smaller than wavelength, a surface plasmon resonance is generated. As a result of this resonance, nanoparticles
produce absorption spectra with peaks depending of particle size as shown below. In contrast to uorescence, SPR
emission spectrum does not have a simple dependence on size [40].
Quantum size e ects: This results in unique optical properties of nano materials owing to spatial con nement of
electrons and holes at nano scale.

Di erence in electrical conductivity

Changes in electrical conductivity of nanostructures and nanomaterials from their bulk counterparts are complex, and
based on di erent mechanisms. These distinct mechanisms can be generally grouped into four cateogories:

Surface scattering including grain boundary scattering

Quantized conduction including ballistic conduction
Coulomb charging and tunneling
Change of microstructure

Also, increased perfection, such as reduced impurity, structural defects and dislocations would a ect the electrical
conductivity of nano structures and nanomaterials.

Transfer of Ferromagnetism to Supermagnetism at nano scale

Ferromagnetism of a body or substance refers to its high susceptibility to magnetization, the strength of which
depends on that of the applied magnetizing eld, and that may persist after removal of the applied eld.
Ferromagnetic particles get unstable when particle size reduces below a certain value. Surface energy provides
su cient energy for domains to spontaneously change polarization directions. As a result, ferromagnetic materials
become paramagnetic (very weakly attracted by the poles of a magnet, but not retaining any permanent magnetism).
However, nanometer-sized ferromagnetics turned to paramagnetics behave di erently from conventional
paramagnetics and are referred to as supermagnetics.

Self-puri cation
Self puri cation is an innate thermodynamic property of nanomaterials. Heat treatment increases the di usion of
impurities, intrinsic structural defects and dislocations, and they can be easily pushed to nearby surfaces. Increased
perfection a ect physical and chemical properties and may enhance them many times which is not observed in bulk
materials.

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