2

Biomimetics

María Vallet-Regí
Departamento de Química Inorgánica y Bioinorgánica, Facultad de Farmacia,
Universidad Complutense de Madrid, CIBER de Bioingeniería, Biomateriales y
Nanomedicina (CIBER-BBN), Spain

2.1 Biomimetics

For millions of years, living creatures have used and perfected biomineral-based materials
with outstanding properties.
Nature has designed its materials and structures, which generate variability through muta-
tion and recombination processes, and then the selection mechanisms favored the optimal
solutions for each biological environment. Some examples of such processes would be
microskeletons, biomagnets, teeth, shells, and bones.
The term biomimetic is generally used to describe the understanding of those solutions
found by Nature to solve each challenge, and our use of them as a source of inspiration to
solve in turn our technological challenges (Figure 2.1).
Biomimetics could therefore be considered as the technology transfer between Nature
and the man-made artificial world.
We can also find many examples where man copied from Nature, such as the Lotus effect
based on the self-cleaning ability of Nelumbo nucifera leaves, which allowed the design
and development of self-cleaning surfaces which are nowadays present in many building
materials.
Another example of biomimetics can be found in the study of particular features of certain
insects and other creatures in terms of their nanostructure. For instance, lizards rely on
nanostructure to move freely on vertical surfaces or to walk upside down. This is possible
because the lizard’s feet are coated with countless thin hairs, each of them ramified in
spatula-ended filaments with dimensions in the nanometer range. These structures follow
the surface roughness; hence the total contact surface of a lizard’s foot is much larger than
the equivalent surface on other species without said nanostructures.

Bioceramics with Clinical Applications, First Edition. Edited by María Vallet-Regí.

© 2014 John Wiley & Sons, Ltd. Published 2014 by John Wiley & Sons, Ltd.
18 Bioceramics with Clinical Applications

Figure 2.1 In the kingdom of vertebrate animals, nature fabricates hard tissues (bones and
teeth). In the botanical kingdom, we find instead non-adherent systems

Homing pigeons or bees find their way over the earth’s crust thanks to magnetite nanopar-
ticles embedded in their tissues; Nature provides a beautiful model for nanobiosensors.
Additional examples can be found in butterfly wings and in the shells of certain beetles.
The colors of those wings and shells are not due to pigmentation. The color stems from the
vast amount of tiny nanostructured scales which reflect the incident light in different ways.
And finally, our very own bones, nanocomposite materials with such amazing mechanical
properties that made them the source of inspiration in the fields of engineering and cement
production for the building industry.

2.2 Formation of Hard Tissues

If we focus on how Nature deals with the production of hard tissue, the first conclusion
would be that biomineralization processes mainly use calcium and silicon combined with
carbonates, phosphates, and oxides. Bone, for instance, is formed by such biomineraliza-
tion processes, natural sequences of physical-chemical reactions that yield the formation
 Biomimetics 19

Osteoblastic cells + Ca

Organic MATRIX + Ca

Phosphatase
PO43−
ATP

Amorphous calcium phosphate

Biological apatatites
Ca8.3 0.7(PO4)4.3(HPO4,CO3)1.7(2OH,CO3)0.15
-Variable composition
-Nanocrystalline: 25–50 nm
-Ca2+ deficient
-Presence of CO32−
1.7 -Structural disorder

enamel
bone
26 30 34 2θ

26 30 34 2θ
dentine
26 30 34 2θ

100 μm

Figure 2.2 Hard tissues in vertebrates are mainly formed by biological apatites (See insert for
color representation of the figure)

of hard tissues in vertebrates or protective tissues in invertebrates and inferior zoological

species (see Figure 2.2). As a result, natural composites are formed, which often feature
exceptional mechanical properties impossible to obtain from pure materials otherwise.
The inorganic phase of our bones is an apatite-like phase. Its structure has the special
ability to accommodate several different ions in its three sublattices. Bone apatite can be
considered basic calcium phosphate. Bones of vertebrate animals are organic–inorganic
composite materials which can be simply described as follows: the inorganic component
is carbonated and calcium deficient nonstoichiometric hydroxyapatite; these biological
apatite crystals are nanometric in size, ranging from 25 to 50 nm. Such crystals grow at
the mineralization sites of the collagen molecules, which are grouped together forming
collagen fibers. Furthermore, a certain hierarchical bone porosity is necessary for several
physiological functions performed by the bone.

2.3 Biominerals versus Biomaterials

A deep understanding of biomineralization and biomimetics is essential to design and

obtain artificial biomaterials aimed at human body repair. The rules of Nature to produce
biominerals are extremely different from those governing mineral growth on Earth’s crust.
20 Bioceramics with Clinical Applications

To put it simply, biomineralization is the formation of an inorganic solid within a

biological system, and it takes place through a precipitation reaction in water solution; as
such, it involves three steps of supersaturation, nucleation, and growth, controlled by the
living species in question. The four most common phases in living beings are displayed in
Figure 2.3.
The biological activity of cells involves a continuous matter exchange with their envi-
ronment, collecting nutrients, and releasing waste products.
There is no biological control over the excretion in these processes known as biologically
induced mineralization, yielding particles with various sizes and morphologies. This is, for
instance, the kind of mineralization performed by certain sulfate reducing bacteria.
On the other hand, each step of the biomineralization process can be genetically con-
trolled, which is then known as biologically controlled mineralization. It is the most com-
mon and important type of biomineralization yielding crystals with homogeneous size and
morphology, arranged in a given way in each living species.
Biominerals are a product of cellular activity. When Nature produces them, it is done
within a well-defined space, and the product is not a simple inorganic solid (Figure 2.4).
The analysis confirms that they always contain organic matter; this content can vary widely,
from less than 1% to almost 40%; their chemical nature and relation to the mineral phase
can also be very different. In some cases, the organic portion of the biomineral may be a
simple film coating an inorganic crystal, while in others it may constitute a matrix intrin-
sically linked to the mineral phase.

HYDROXYAPATITE OPAL
CALCITE ARAGONITE
Ca10(PO4)6(OH)2 SiO2.nH2O
CaCO3 CaCO3
AND “Ca Phosphates”

• Inorganic phase in * algae

* Eggshell mammal hard tissues * Basic zoological
* Hard tissues in invertebrates * vertebrates species

Shells of molluscs: protection Bones of vertebrates:

support

CaCO
3
CaCO CaCO CaCO3
3 CaCO
3
3 CaCO3 CaCO3
CaCO CaCO3
CaCO 3 C aCO3 CaCO3
3
CaCO CaCO3 CaCO3 cells
CaCO 3 CaCO3
3 CaCO CaCO3
3 CaCO3

Organic matrix: Inorganic component:

Inorganic component:
- aragonite nanocrystals
- Type I collagen - Apatite nanocrystals
- Glycoproteins
Organic matrix: - Mucopolysaccharides
- cells
- proteins

Figure 2.3 The four most common inorganic phases in biomineralization processes. In all
cases, they appear embedded in an organic matrix to form protection systems (molluscs, shells)
or structural systems (vertebrates) (See insert for color representation of the figure)
 Biomimetics 21

Biominerals

Inorganic Organic
component component

Si Ca
dioxide phosphates Ca protein
carbonates vesicles matrices
25 nm

apatite

Figure 2.4 Biominerals exhibit mainly two components, organic and inorganic, respectively

Using common terms in materials science and engineering, most biomaterials can be
defined as true composites. This feature is responsible for their optimal mechanical prop-
erties, unequaled by synthetic materials. The study of the structure of biomaterials and
biomineralization processes not only provides important biochemical information, it can
also lead to new strategies for scientists and engineers in the development of novel industrial
materials (Figure 2.5).
For all of the above, it is crucial to understand the mechanism of mineralization in order
to mimic it in material production processes and to obtain artificial devices able to replace,
repair, or even better, regenerate damaged tissues in the human body.

Biomineral
Biomaterial

Figure 2.5 Biomaterial versus biomineral. The artificial and the natural routes
22 Bioceramics with Clinical Applications

Recommended Reading
1. Kuhn, L.T., Fink, D.J. and Heuer, A.H. (1996) Biomimetic strategies and materials pro-
cessing, in Biomimetic Materials Chemistry (ed S. Mann), John Wiley & Sons, Inc.,
New York, p. 41.
2. Mann, S. (1996) Biomimetic Materials Chemistry, Wiley-VCH Verlag GmbH, Wein-
heim.
3. Mann, S., Webb, J. and Williams, R.J.P. (eds) (1989) Biomineralization, Chemical and
Biochemical Perspectives, Wiley-VCH Verlag GmbH, Weinheim.
4. Vallet-Regí, M. and Arcos-Navarrete, D. (2008) Biomimetic Nanoceramics in Clinical
Use: From Materials to Applications, Royal Society of Chemistry, Cambridge.