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 Nanotechnology – nanomaterials, nanoparticles and
multifunctional core/shell type nanostructures
Marcin Runowski* – Department of Rare Earths, Faculty of Chemistry, Adam Mickiewicz University,
Poznań, Poland
Please cite as: CHEMIK 2014, 68, 9, 766–775
Introduction to “nanoworld”
Nowadays, we live during an intensive development of science
known as nanotechnology, which is closely related to chemistry of
colloids. The average size of particles forming a given colloid is often
in the range of 1–1000 nm (1 nm = 10-9 m). Due to the small size, such
nanoparticles can form stable colloidal solutions, which is important in
case of bioapplications, tracing techniques and materials engineering.
There are many definitions of nanoparticles. One of them says that,
when a given material is composed of particles, whose at least one
dimension is smaller than 100 nm, than such material can be called
as „nanomaterial”. Another definition determines „nanomaterial” as
a material which after „miniaturization” to nanoscale reveals altered
physicochemical properties in comparison to the bulk product
(macroscopic) [1, 2].
Properties of nanomaterials
The alterations of physicochemical properties of nanomaterials
are often caused by quantum confinement of electrons in small
nanoparticles, and by an increased ratio of surface/near surface atoms
or ions to the ones localised inside a given particle. The result of
that is large specific surface area of nanomaterials, resulting in an
increased number of unoccupied coordination sites, defects and
crystal lattice strains. That is why, surface atoms and ions are situated
in different coordination environment, which results in changed
physicochemical properties of many nanomaterials. The examples of
such changes are following: alternation of spectroscopic properties,
melting point, density, solubility, mechanical properties (friction,
ductility, elasticity), electrical conductivity, surface tension, different
response to the applied magnetic field, changes in crystal structure
(some structures are stable only in nanoscale) or increased catalytic
activity of nanomaterials [1, 3÷7].
Quantum confinement
Quantum confinement is an effect occurring in nanoscale, which can
be predominantly observed in semiconductors, when their particle size
is smaller than 10 nm. More precisely, this size depends on Bohr radius
of exciton in a given material [8, 9]. Semiconducting nanostructures
in which such phenomenon occurs, restricted in one dimension, are
known as “quantum wells” [10], restricted in two dimensions are known
as „quantum wires” [11], and in three dimensions are called „quantum
dots” [12, 13]. A spectacular effect of the mentioned phenomenon can be
multicolour luminescence of quantum dots. When such nanostructures
are irradiated with UV light at a specified wavelength, the emission
in a visible range occurs. The emission depends on nanoparticle size.
In first approximation, this can be explained by an increase of band gap,
i.e. the distance between HOMO-LUMO orbitals (Highest Occupied
Molecular Orbital – Lowest Unoccupied Molecular Orbital), together
with particle size decrease. It means, that the smaller nanoparticles
of given semiconductor e.g. CdSe, CdS czy ZnO, under UV light
irradiation will exhibit luminescence shifted towards blue colour, and
bigger ones towards red colour [14, 15].
Corresponding Author:
Marcin Runowski, M.Sc., e-mail: runowski@amu.edu.pl
nr 9/2014 • tom 68
science • technique
Surface plasmons
Another example of phenomenon which can be observed only in
nanomaterials is a change of colour of nanostructural metal particles,
e.g. gold, which together with size decrease, can change their colour
from blue (bigger particles) to red (smaller particles). This phenomenon
is caused by resonant absorption of radiation by oscillating, surface
valence electrons – “surface plasmons”, in metal nanoparticles. The
result of this phenomenon is differential absorption of visible light,
dependent on nanoparticle size. This effect usually occurs when
their size is smaller than 150 nm (however, it disappears in the case
of too small particles), and it is strongly dependent on the product
morphology [16, 17].
Superparamagnetism
In case of magnetic properties of nanoparticles, the change
which occurs in nanoscale is superparamagnetism. This phenomenon
occurs in ferro- and ferrimagnetics, after reduction of their particles
to nanoscale (usually from several to several tens of nanometres). The
critical size when the mentioned phenomenon occurs, depends on the
material type, more precisely on the value of its magnetic anisotropy,
which in turn depends on chemical composition, crystal structure and
morphology. Superparamagnetic materials do not exhibit remanence
(postmagnetization which remains when the external magnetic
field is off), and their coerce (the value of magnetic field necessary
for reduction of the remained magnetization of material to zero) is
equal to zero. Such behaviour results in a so called superparamagnetic
limit. This is a critical particle size, which determines the maximal
capacity of data carriers based on magnetic memories. The well-
known example are magnetite – Fe3O4 nanoparticles, which become
superparamagnetic when their size is reduced below ≈ 12 nm. When
the magnetic field is off, such nanoparticles lose their magnetization,
because of the magnetic moments averaging of single crystals (in this
example every grain is composed of a single magnetic domain), caused
by thermal energy [18, 19].
Toxicity of nanoparticles
Currently, the very important issue in case of nanoparticles
research, is their toxicity. As was mentioned previously, nanomaterials
often reveal different properties in comparison to their counterparts
in macroscale (bulk material), which influence also their biological
properties. Unfortunately, this change of properties is often unfavourable
in case of bioapplications, due to the occurrence of cytotoxicity of small
nanoparticles. The materials normally neutral for living organisms,
often exhibit significant increase of their cytotoxicity, when the size
of their particles is reduced to nanoscale [20, 21]. Such toxicity can
be caused by an easier, enhanced release of heavy metal ions from the
nanoparticles surface, as in case of quantum dots such as CdSe, CdTe
or PbS [22, 23]. The cytotoxicity of nanomaterials can be also induced
by the porosity of nanoparticles, tendency to agglomeration, significant
chemical affinity to the numerous of biostructures or increased
chemical reactivity of their surface [24, 25]. An important role play
also physical and mechanical factors, such as the size comparable
or smaller than biostructures. They can be easily suspended in air
forming harmful suspensions of dust, which can be inhaled by human,
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 and cause pneumoconiosis and lung cancer [26, 27]. Because of the
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small size, nanoparticles can be absorbed via endocytosis by some of
the cells of living organisms and accumulate there by attaching/binding
with proteins, cell membranes and other biostructures [25]. The
mentioned processes can cause cells and tissues damages by increased
oxidation stress, blocking of ionic channels or mechanical damage of
cell membrane and other organelles [28, 29]. These factors may also
interrupt cells proliferation, resulting in their dying or an uncontrolled
growth, which can lead to the formation of tumour [30].
Preparation methods of nanostructures
There are many methods of nanostructures preparation, which
can be divided into two sorts, namely the „top-down” and „bottom-
up” methods [1, 31, 32]. The first one is based on comminution of the
bulk, macroscopic materials to nanoparticles, i.e. their counterparts in
“nanoscale”. Crumbling, ball milling and different kinds of lithography
are known as „top-down” methods.
Much better results (less defects and narrower size/shape
distribution of grains) provide „bottom-up” methods, which are
based on nanocrystallites growth and its controlled cessation, by the
formation of nanostructures “atom by atom”. This process occurs
by self-assemble of single atoms into larger groups – clusters, and
their further aggregation to nanoparticles. The mentioned methods
are based on nanomaterials preparation via chemical synthesis, and
thanks to the utilization of appropriate physical processes, as well. The
examples of frequently used „bottom-up” methods are: precipitation
of nanoproducts in solutions, deposition of reactants layer-by-layer
(Langmuir-Blodgett technique), decomposition of organic precursors,
synthesis under hydrothermal conditions, hydrolysis and subsequent
condensation of reactants, surface redox exchange, sputtering in
vacuum, condensation in liquid or gaseous phase etc. The scheme of
nanoparticles preparation by „top-down” and „bottom-up” methods
is presented in Figure 1.
Fig. 1. The scheme of nanoparticles synthesis by „top-down” and
„bottom-up” methods
Luminescent nanostructures
The structures exhibiting luminescence were and still are
intensively studied, because they find applications in many areas of
science and technology [33]. In the past, the organic dyes were the
most common phosphors because of their large molar absorption
coefficient of ultraviolet light. However, they turned out to be unstable,
because of their low resistance to long-term exposure to light and
facile decomposition by oxidation. Such dyes simply bleach after
some time, and illuminate weaker and weaker. That is why, quantum
dots exerted significant interest. Nanostructured quantum dots are
resistant to photodegradation, high temperature and exhibit intense
luminescence due to the broad spectral range, in which they can absorb
radiation, resulting in the electrons excitation and their subsequent
radiative relaxation [34]. However, their fundamental drawback is
a significant cytotoxicity, caused by the presence of heavy metals in their
structure [22]. The promising group of phosphors seems to be various
inorganic chemical compounds such as oxides, fluorides, oxofluorides,
borates, phosphates and vanadates, doped or composed of rare earth
elements. Such phosphors are resistant to photodegradation, high
temperature, redox processes, aggressive agents or UV radiation.
They also reveal much lower toxicity in comparison to quantum dots.
Thanks to this, they can be used in bioapplications [35÷38]. What is
772 •
more, they exhibit intensive, multicolour luminescence, having narrow
emission bands. The intensive luminescence in these systems is caused
by energy transfer and charge transfer effects [39, 40]. The phosphors
based on rare earth elements can be applied in plasma display panels
[33], detection systems [41], biomarkers [42, 43], optoelectronics
[44], lighting [33], luminescent tracing [45] and as luminescent cores in
the core/shell type nanostructures [35, 36].
Magnetic nanoparticles
The desired magnetic properties of the compounds are important
in case of many sophisticated composite nanomaterials. In this area
of magnetic nanomaterials, ferri- and ferromagnetics are mainly
utilized [46]. Spherical, hybrid core/shell type nanostructures having
magnetic core, e.g. Fe3O4/SiO2 can be applied as compounds used
for the purification of water and other media from heavy metal ions,
such as Hg2+, Pb2+, Cd2+ [47]. Their removal becomes possible
thanks to the high affinity of appropriately functionalized shell to the
mentioned ions. By the magnetic field manipulation, the nanoparticles
having appropriately modified surface can bind to the cell membrane
of bacteria, viruses or attach to the selected cells in an organism,
which were affected by a disease [48]. Afterwards, such combinations
can be removed from the living organism or selectively destroyed.
Small superparamagnetic nanoparticles of magnetite are used as
contrast agents in MRI (Magnetic Resonance Imaging) [49]. When such
nanoparticles are modified, coated with proper shell, their contrast
properties and stability can be additionally enhanced.
Core/shell type nanostructures
Core/shell type nanoparticles are composed of at least two
separate phases having different chemical composition or structure.
Thanks to this, such hybrid material becomes multifunctional, because
it simultaneous reveals the properties of the core and the shell. Figure
2 depicts the scheme of an exemplary core/shell type nanostructure.
Fig. 2. The scheme of an exemplary core/shell type nanostructure
Usually, an inorganic nanocore coated with a single or multi
shell is a centre of a given particle. The external shell/shells reveal
different structure or chemical composition, in comparison to the
nanocore. The properties of the core can be modified depending
on the further product application. It can be magnetic like magnetite
– Fe3O4 [19, 47], exhibit luminescence properties as semiconducting
quantum dots – e.g. ZnO, CdSe [50, 51] or nanocrystalline lanthanide
(Ln3+) doped phosphors – e.g. CeF3:Ln3+, LaPO4:Ln3+ (Ln = Eu, Tb,
Sm, Gd) [35, 52 – 54] and exhibit other desired functions. The shell
can be an organic polymer [42, 55] as well as an inorganic compound
like TiO2 or SiO2 [35, 36, 56].
Preparation methods of core/shell type nanostructures
There are numerous methods to prepare core/shell type
nanomaterials. The most frequently applied methods are based on:
precipitation of the desired compound (shell) on the core surface,
redox exchange (surface oxidation/reduction), surface layer leaching or
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capping the core surface with organic modifier molecules is a solution.
The zol-gel techniques, such as Stöber method [57] are very often
used ones, as well. They are based on hydrolysis of the appropriate
precursors of the shell (silane derivatives), and their subsequent
condensation on the core surface, which has been previously dispersed
in the solution. Figure 3 presents the chosen methods of preparation of
core/shell type nanostructures.
Fig. 3. The chosen synthesis methods of core/shell type nanoparticles
The properties of nanoshell and surface modification
Small nanoparticles have large surface-to-volume ratio, so they are
very sensitive to redox reactions, pH change, impact of aggressive agents
and environment. That is why, in order to avoid product decomposition
or deterioration of its specific physicochemical properties, it should be
coated with an external protective shell, which results in a formation of
the mentioned core/shell type nanostructures [58, 59]. Such shell can
be inert or active to the desired functional groups or it can be modified
according to the intended applications. The shells are often modified
by coupling with different organic molecules, which can be bioactive
and act as linkers, antigens and other specific species, for bioapplications
[42, 60]. The modification can be performed by the formation of
permanent covalent bond (e.g. -Si-CH2-NH2) [35, 61], electrostatic
interactions or Van der Waals forces [62]. Such functionalized core/
shell type nanostructures can exhibit selective affinity to the desired
moieties and active sites in a cell. Thanks to this, it is possible to use
them in novel targeted therapies as drug carriers or biomarkers [63].
The consequence of the modification can be alteration of biological
properties of such nanoparticles, e.g. decrease in their cytotoxicity [35,
64]. Here is worth to note, that there are known also yolk/shell type
nanostructures which are similar to the core/shell type ones. However,
the difference is an “empty core” of the yolk/shell type nanoparticles.
Such effect can be obtained just during synthesis or by appropriate
post-treatment processes. The mentioned yolk/shell nanostructures
can find applications as novel, very efficient and selective drug carriers
in targeted therapies (drug molecules encapsulated in the empty core
and selectively released in a designed place).
As was mentioned above, the advanced core/shell type
nanostructures are a new class of composite materials featured with
a plenty of properties hitherto unknown. The benefits from application
of such structures result of their bi- or multifunctionality, and thanks
to this they combine the properties of the core and the shell in a single
material. These multifunctional nanoparticles can simultaneously exhibit
interesting properties such as multicolour tuneable luminescence
and response for an applied magnetic field. What is more, these
nanomaterials may reveal significant bioavailability, biocompatibility
and selective binding to the desired structures. Figure 4 shows the
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simultaneous green emission and response for the applied magnetic
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field of the luminescent-magnetic core/shell type nanoparticles
composed of Fe3O4/CeF3:Gd3+, Tb3+/SiO2. The images were taken
in a day-light and under UV light irradiation, before and after magnet
capture. Figure 5 presents transmission electron microscopy (TEM)
images of luminescent core/shell type nanostructures having surface
modified with amine groups (dark cores and light shells).
Fig. 4. Green emission under UV light (λex = 254 nm) and response
for the applied magnetic field of core/shell type nanoparticles
– Fe3O4/CeF3:Gd3+, Tb3+/SiO2; before (a, b) and after magnet capture
(c, d), in a day-light (a, c) and under UV light – 254 nm (b, d)
Fig. 5. TEM image of surface modified core/shell type nanoparticles
– CeF3:Tb3+/SiO2/NH2
Such nanomaterials can be potentially applied for imaging/
detection of the desired structures and their simultaneous magnetic
separation. Thanks to the mentioned properties, these compounds
have significant possibilities of application and can be used in many
areas of science and industry e.g. in medicine, biochemistry, forensics,
materials engineering, nanobioengineering or in industry of functional
and everyday use materials. However, core/shell type nanomaterials
are synthesized in a laboratory scale, mainly because of the expensive
synthesis process, long fabrication time and frequent problems with
repeatability and reproducibility of the given synthesis method.
Summary
Nanotechnology is a rapidly developing discipline, which
allow the fabrication of novel, hitherto unknown nanostructured
materials, featured with unique properties and multiple possibilities
of application. Such nanomaterials can exhibit altered spectroscopic,
magnetic, structural and biological properties. What is more, some of
the nanoparticles like multifunctional core/shell type nanostructures
can reveal simultaneously several desired features, e.g. luminescence,
magnetism, decreased cytotoxicity and enhanced reactivity/affinity to the
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 desired structures. An important issue concerning the development
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of nanotechnology is a permanent enhancement and unification of
nanomaterials synthesis and a modification of their surface. Thanks
to this, the nanomaterials revealing improved homogeneity and
monodispersity can be obtained. The essential aspects concerning
nanomaterials preparation are related to the synthesis duration and
its cost (fast and inexpensive syntheses are preferred), stability of the
products, facile reproducibility and low toxicity of the solvent used,
as well as reactants and products of the synthesis.
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Luminescent Nanoparticles Based on Lanthanide Doped Fluorides
(LaF3:Ce3+, Gd3+, Eu3+), Obtained in the Presence of Different Surfactants.
J. Alloy. Comp. 2014, 597, 63–71.
54. Runowski M., Balabhadra S., Lis S.: Nanosized Complex Fluorides Based on
Eu3+ Doped Sr2LnF7 (Ln=La, Gd). J. Rare Earths 2014, 32, 242–247.
55. Ramli R. A., Laftah W. A., Hashim S.: Core–shell Polymers: A Review. RSC Adv.
2013, 3, 15543–15565
56. Pang S. C., Kho S. Y., Chin S. F.: Fabrication of Magnetite/Silica/Titania Core-
Shell Nanoparticles. J. Nanomater. 2012, 2012, 1–6.
57. Stöber W.: Controlled Growth of Monodisperse Silica Spheres in the Micron
Size Range. J. Colloid Interface Sci. 1968, 26, 62–69.
58. Park J.-N., Zhang P., Hu Y.-S., McFarland E.: W. Synthesis and Characterization
of Sintering-Resistant Silica-Encapsulated Fe3O4 Magnetic Nanoparticles Active
for Oxidation and Chemical Looping Combustion. Nanotechnology 2010, 21,
225708–225716.
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59. Runowski M., Grzyb T., Lis S., Bifunctional Luminescent and Magnetic Core/
science • technique
shell Type Nanostructures Fe3O4@CeF3:Tb3+/SiO2. J. Rare Earths 2011,
29, 1117–1122.
60. Warren C. W., Chan P. D.: Bio-Applications of Nanoparticles. Springer S,
New York, 2009.
61. Mello M. R., Phanon D., Silveira G. Q., Llewellyn P. L., Ronconi C. M.:
Amine-Modified MCM-41 Mesoporous Silica for Carbon Dioxide Capture.
Microporous Mesoporous Mater. 2011, 143, 174–179.
62. Jal P. K., Patel S., Mishra B. K.: Chemical Modification of Silica Surface
by Immobilization of Functional Groups for Extractive Concentration of Metal
Ions. Talanta 2004, 62, 1005–1028.
63. Yang P., Quan Z., Hou Z., Li C., Kang X., Cheng Z., Lin J.: A Magnetic,
Luminescent and Mesoporous Core-Shell Structured Composite Material as
Drug Carrier. Biomaterials 2009, 30, 4786–4795.
64. Nabeshi H., Yoshikawa T., Arimori A., Yoshida T., Tochigi S., Hirai T.,
Akase T., Nagano K., Abe Y., Kamada H.: Effect of Surface Properties of
Silica Nanoparticles on Their Cytotoxicity and Cellular Distribution in Murine
Macrophages. Nanoscale Res. Lett. 2011, 6, 93–98.
*Marcin Runowski, M.Sc., graduated from Faculty of Chemistry at
Adam Mickiewicz University in Poznań (2012). His bachelor thesis was
awarded with Gold Medal of Chemistry in nationwide competition for the
best bachelor/engineer degree thesis made in 2010/2011 academic year,
and organized by Institute of Physical Chemistry PAS in Warsaw. Whereas,
his master thesis was distinguished to the Janina Janikowa Award, for the
best master thesis made in 2011/2012. Currently, he is a Ph.D. student
in the Department of Rare Earths at the same faculty. In his research
he  deals with the synthesis and characterization of multifunctional
core/shell type nanomaterials, exhibiting luminescence and/or magnetism.
Scientific interests: nanotechnology, synthesis of nanomaterials, surface
modification, cytotoxicity of nanoparticles, luminescence, magnetism,
lanthanide spectroscopy. He is an Author of 11 scientific publications and
48 communications at national and international conferences.
e-mail: runowski@amu.edu.pl, phone: +48 61 829 1346
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