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MSE 598/494 Bio-inspired Materials and Biomaterials MSE 598/494 Bio-inspired Materials and Biomaterials
Instructor: Ximin He
TA: Xiying Chen Email: xchen128@asu.edu
2014-04-03
Lecture 11 & 12. Biominerilaztion
Proteins and Organisms
Lecture 11 & 12. Biominerilaztion
Proteins and Organisms
material/composition?
shapes?

Biomineralization
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More and more functions for synthetic materials
Tissue engineering: regenerative biomedical, hard tissue (bone, enamel)
Advanced Materials: Light weight tough material for building, aircraft, vehicle
Nanomaterials : precise control of nano-spheres, rods, wires, tubes, etc
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Nature
producing mineralised skeletons
for the 550 million years
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Nature evolved to grow superior biominerals
Optical sensing (predator) Mechanical tough (protection)
Photonic color
Self healing
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Diversity
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Biomineralization
Definition: the process that organisms use biomolecules and biological substances to
assemble organized inorganic scaffolds, often to harden or stiffen existing tissues.
Examples: silicates in algae and diatoms, carbonates in invertebrates, and calcium
phosphates and carbonates in vertebrates
Structures
considerable variety of structures, morphologies, and shapes of materials
Underlying Molecular Mechanism?
directed crystal growth occurring at biomolecular interfaces
recruitment of various organic and inorganic building blocks
the specific conditions of the aqueous solution environments
Functions
magnetic sensors in magnetotactic bacteria (Fe
3
O
4
),
gravity sensing devices (CaCO
3
, CaSO
4
, BaSO
4
),
iron storage and mobilization (Fe
2
O
3
H
2
O in the protein ferritin)
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What you will learn in the next 90 minutes?
Lecture 11. Biomineralization - Proteins
Natural biominerals: Nacre, Bone
Protein Template for Artificial Nacre, Synthetic Bone
Cellular membranes template (option for Lit Rev Presentation)
Lecture 12. Biomineralization - Organisms
Virus: M13 phage, T7 phage
Bacterial Cells
Larger organisms
Applications (M13 phage for self-assembly, photovoltaics)
(option for Lit Rev Presentation)
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Template:
i) proteins
peptide
ii) viruses
bacteria
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MSE 598/494 Bio-inspired Materials and Biomaterials MSE 598/494 Bio-inspired Materials and Biomaterials
Instructor: Ximin He
TA: Xiying Chen Email: xchen128@asu.edu
2014-04-03
Lecture 11. Biominerilaztion
Protein- and peptide-associated biomineralization
nacreous layer:
iridescent
strong, resilient, tough
A Story of Nacre
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Fun Fact: Usage of Nacre
Architecture - mosaic with durable and glossy surface
Marble or tile base: nacre tesserae is cut into shapes and laminated to
a ceramic tile or marble base
Light weight material: interior floors, exterior and interior walls,
countertops, doors and ceilings
Fashion:
Decoration:
Watch
musical instruments
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Pearly Kings and Queens
(an organised charitable tradition
of working class culture in London)
Delicate Beauty?
Unique properties:
Optical: ~80% total transmission of visible light (window panel)
Mechanical: penetration resistance through a variety of energy-dissipating
mechanisms, by increasing energy dissipation density (0.290 nJ m
3
) by an
order of magnitude relative to single-crystal geological calcite (0.034 nJ m
3
)
Ortiz, et al. Nature Materials 2014
pervasive nanoscale deformation twinning
(width ~50 nm)
windowpane oyster (~99 wt% calcite)
a layered assembly of elongated
diamond-shaped calcite crystals
Mechanism: catalyses a series of additional inelastic energy dissipating
mechanisms (intracrystalline nanocracking, nanograin formation and reorientation)
Extremely tough and lightweight armour for US soldier!
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Nacre
A remarkable organicinorganic composite biomaterial
Structure & Composition:
Ordered inorganic layers of calcium carbonate platelets separated by
porous organic polymers such as chitin
Properties:
Optical iridescent sheen
Mechanical tough, resilient to damage, due to highly efficient dissipation
of cracks and mechanical stress
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brick wall structure comprising
Ca(CO
3
) crystals and biopolymer mortar
Mimicking the Biomineralization
Organic Template Inorganic Mineral
1. Biomimetic templates
Polyaspartic acid adsorbed on a sulfonated PS film as a scaffold for CaCO
3
Langmuir manolayers of fatty acids on aqueous subphases
Self-assembly monolayers (SAMs) on solid substrates
Acidic macromolecules:
Polysaccharides
(glyco)proteins
Aspartatic acid
Glutamic acid
Phophate moities
Calcium carbonate
Silica
apatite
2. Directing Effects
How to induce
Oriented Nucleation
with acidic groups on
surfaces
Carboxylic
Phosphate
Sulfate
3. Precise control of
composition,
organization,
morphology,
other properties
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Artificial Nacre the toughness
The same structure that gives seashells their strength
has been replicated in glass
Structure: lasers to create an analogue of nacre by engraving networks
of wavy 3D "micro-cracks" in glass.
Property:
Treated glass is 200 times tougher than untreated glass.
Mechanism: when the slides were subjected to an impact, the micro-
cracks absorbed and dispersed the energy, keeping the glass from
shattering.
15 Franois Barthelat, et al. Nature Communications 2014
Artificial Nacre the structure
Al
2
O
3
and PMMA
Exceptional strength and
toughness, ascribed to
the specific composition,
the microscopic layered structure of
the particulates
Launey, M.E. et al.,
Designing highly toughened hybrid composites through natureinspired hierarchical complexity,
Acta Materialia 2009 57, 29192932.
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Artificial Nacre the growth
The first successful attempt to replicate nacre, using CaCO
3
Mimicking the growth composite, structure, and property:
Calcium carbonate-based nacre in the laboratory by mimicking its natural
growth process with layer-by-layer assembly
17 Ullrich Steiner, Nature Communications 2012
Artificial Nacre the growth
Polymer-mediated Mineral Growth:
early-stage crystallization through
single PVP pores in a trilayer of
cal
org
/organic/cal
org
Ullrich Steiner, Nature Communications 2012
(scale bar: 500 nm)
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Protein- and peptide-associated biomineralization
Acidic Proteins - mineralization templates
Negatively charged amino acids: particularly glutamate (Glu)
Mechanism:
To recruit and bind inorganic cations, such as calcium, thereby initiating the
mineralization process.
Artificial biomineralization:
Their Nature and Organization Mineral Assembly
Utilize surfaces containing acidic amino acids or negatively-charged
moieties as synthetic templates for artificial biomineralization
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peptide-mimics template - Peptoid
Peptoid structures respective
distinct CaCO
3
crystal
morphologies produced upon
incubation of the peptoids with
Ca
2+
and sequestered CO
2
.
Biologically-induced
inorganic materials:
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Chen, C.L. et al., J. Am. Chem. Soc. 2011 133, 52145217.
Biological molecule:
recognition units/domains
nucleation sites
molecular facets activating crystallization
aid overcoming energy barriers
Non-biological substances bind
Mineral assembly
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Repair and Reconstruction of Tooth Enamel
Enamel: the protective layer of the tooth
Challenge: complex needle-like structure comprising tiny crystallites of apatite; limited
supply of natural enamel-template proteins(enamelins/ameliogenins) as seeding agents
Approach: Regenerated layers of crystalline apatite formed through bridging by the
negatively-charged glutamic acid
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Natural:
crystalline apatite
Ca
10
(PO
4
)
6
(OH)
2
Artificial:
Li, L. et al., Adv. Mater. 2011, 23, 46954701
Bone Formation
Bone formation: similar hierarchical mineralization of calcium and phosphate
ions forming hydroxyapatite crystals via collagen matrix
physical properties of collagen Bone morphology & internal organization
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Zhang, Z. et al., Applications of functional surfactants,
Curr. Opin. Coll. Interface Sci. 2002 7, 267275.
collagen-mimic peptide-amphiphile fibers:
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The natural growth dynamic environmental cues
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Abrupt switches in marine shell pattern
Hierarchical, complex
Continuously changing chemical cues
Significance & Motivation:
Top-down lithography V.S. bottom-up
Shed light on biominerilization process in natural evolution, yet unpredictable
Rationally design and actively shape self-assembly by manipulating
microenvironment, epitaxy, inorganic-organic additives, etc. to direct write and
sculpt arbitrary 3D hierarchical structures
Rationally Designed Complex Hierarchical Microarchitectures W. Noordiun, et al. Science 2013
Rational Design
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Novel strategy:
Exploited to program a variety of elementary
growth patterns:
Ba
2+
+ CO
2
+ H
2
O BaCO
3
+ 2H
+
SiO
3
2
+2H
+
SiO
2
+H
2
O
By diffusion of CO
2
in a solution of BaCl
2
and Na
2
SiO
3
Responsive growth of BaCO
3
-SiO
2
structures, toward or away from the bulk solution
Three reaction regimes under two distinct growth modes: continuous and
discrete modulations, controlled by CO
2
concentration, pH, and temperature
Stems SrCO
3
-SiO
2
(pH 11.8)
tulips BaCO
3
-SiO
2
(4
o
C, pH 11)
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Rational Design
CO
2
Flux:
amount direction (orientation of sample)
Rationally Designed Complex Hierarchical Microarchitectures W. Noordiun, et al. Science 2013
Rationally Designed Complex Hierarchical Microarchitectures W. Noordiun, et al. Science 2013
a combinatorial matrix
of morphologies by
changing the orientation
of the substrate in
distinct growth steps to
stack different
morphologies on top of
each other. (Strontium
Carbonate) SrCO
3
-SiO
2
Stem, (Barium
Carbonate) BaCO
3
-
SiO
2
vases.
Rational Design
SrCO
3
-SiO
2
vases containing SrCO
3
-SiO
2
stems (green)
- subsequently opened with a CO
2
pulse (blue)
Rhythmical pulsing of CO
2
in the Ba-Si solution
controllably produces ripples in the growing structures
that can be used to write messages in Morse code.
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MSE 598/494 Bio-inspired Materials and Biomaterials MSE 598/494 Bio-inspired Materials and Biomaterials
Instructor: Ximin He
TA: Xiying Chen Email: xchen128@asu.edu
2014-04-01
Lecture 12. Biominerilaztion
Organism-templated biomineralization
Organism-templated biomineralization
entire organisms serving as templates
algae, virus and cyanobacteria
bacterially-induced calcification has been proposed as a promising biogenic
route for sequestering atmospheric carbon dioxide and for carbon storage
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Brome mosaic virus (BMV) capsids:
Virus-like particles (VLPs) comprising
different sizes of inorganic cores
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Tobacco mosaic virus (TMV) templated Biomineralization
inorganic deposits grown on the surface of TMV. (a) TMV coated
with iron oxide, initial product; (b) TMV coated with iron oxide, 6
months incubation.
TMV coated with silica; the arrows indicate the lengths of individual
viral particles, suggesting head-to-tail arrangement of the viral rods.
29 Shenton, W. et al., Adv. Mater. 1999 11, 253256.
M13 phage
M13 phage: a bacteria-infecting virus, composed of a single-stranded
DNA encapsulated by several coat proteins
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Flynn, C.E. et al., Viruses as vehicles for growth, organization
and assembly of materials, Acta Materialia. 2003 51, 58675880.
coat proteins
binding and nucleation of
different inorganic substances
peptides
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Phage-library for biomineralization templates
Phage-library technology for identification of effective biomineralization
templates
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1) A library of recombinant phages,
comprising different peptides
displayed at the phage coat proteins
2) reacted with inorganic substances
3) phages interacting with the inorganic materials,
or inducing mineralization, are isolated
4) most effective biomineralization-inducing
phages are selected and sequenced
Flynn, C.E. et al., Viruses as vehicles for growth, organization and assembly of materials, Acta Materialia. 2003
Liquid crystalline quantum dots through M13 library screening
the phage displaying the peptide with the highest affinity was
isolated and amplified
concentrated solution of the phage-QD complexes adopts a
liquid crystalline organization -- optical and spectroscopic
applications
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Flynn, C.E. et al., Viruses as vehicles for growth, organization and assembly of materials, Acta Materialia. 2003
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T7 bacteriophage
Spherical viruses, icosahedron-shaped bacteriophage
Deposition of inorganic substances can be carried out both externally
on the viral coat and inside the particle.
Ghost viruses comprising the T7
capsids without the encapsulated DNA
Metallic cobalt grown inside
the T7 ghost viruses
Liu, et al. J. Magn. And Magnetic Mater. 2006 302, 4751.
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Microorganisms - bacteria
charged amino acids and other functional groups at the cell surface
after the biomineralization process, the bacterial cells are removed
through annealing (high temperature), leaving behind hollow structures in
varied configurations, depending upon the bacterial species encapsulated.
highly uniform ZnO hollow spheres
using the spherical bacterium
Streptococcus thermophilus
Zhou. et al. Micro. Meso. Mater. 2007 100, 322327.
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Microorganisms - diatoms
ZnS:
Diatoms:
Gordon, R. Star Trek replicators and diatom nanotechnology, Trends Biotech. 2003 21, 325328.
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Larger organisms as templates
sea-urchin skeleton - Au replication butterfly-wing microstructures Al
2
O
3
using ALD, for photonic applications
Huang, J. et al., Nano Lett. 2006 6, 23252331. Seshadri R. and Meldrum F. C., Adv. Mater. 2000 12, 11491151.
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Summary
Biomineralization:
molecular mechanism structure function
Lecture 11. Proteins templating
Natural biominerals: Nacre, Bone
Protein Template for Artificial Nacre, Synthetic Bone
Cellular membranes template (option for Lit Rev Presentation)
Lecture 12. Organisms templating
Virus: M13 phage, T7 phage
Bacterial Cells
Larger organisms
Applications (M13 phage for self-assembly, photovoltaics)
(option for Lit Rev Presentation)
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Reading Resources
Prof. Steve Mann
Prof. Joanna Aizenberg
Are glass sponges made of glass?
tricks for turning its brittle, primarily
glass skeleton into strong structures
double-lens design
Brittlestar calcite single crystals -photodetector
genus Euplectella
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Homework of Lecture 11-12
1. Please state the general mechanisms of biomineralization, by
describing the roles of organic, inorganic elements and their
interactions.
Due by 04/08/2014
Hand in hard copy of homework at the TA, Xiying Chen, at the
beginning of the 04/08 class
Please contact xchen128@asu.edu for questions.