Lect 11-12 Biomineralization_print

8/11/2019 Lect 11-12 Biomineralization_print

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MSE 598/494 Bio-inspired Materials and BiomaterialsMSE 598/494 Bio-inspired Materials and Biomaterials

Instructor: Ximin He

TA: Xiying Chen Email: [email protected]

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, etc3

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 calciumphosphates and carbonates in vertebrates

Structuresconsiderable 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

Functionsmagnetic sensors in magnetotactic bacteria (Fe3O4),

gravity sensing devices (CaCO3, CaSO4, BaSO4),iron storage and mobilization (Fe2O3H2O 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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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 toa 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 organisedcharitable 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 m3) by anorder of magnitude relative to single-crystal geological calcite (0.034 nJ m3)

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 byporous organic polymers such as chitin

Properties: Optical iridescent sheen

Mechanical tough, resilient to damage, due to highly efficient dissipationof cracks and mechanical stress

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brick wall structure comprising

Ca(CO3) 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 CaCO3 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 ofcomposition,

organization,morphology,

other properties

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Artificial Nacre the toughness

The same structure that gives seashells their strengthhas been replicated in glass

Structure: lasers to create an analogue of nacre by engraving networksof 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

Al2O3 and PMMA

Exceptional strength andtoughness, ascribed to

the specific composition,

the microscopic layered structure ofthe particulates

Launey, M.E. et al.,

Designing highly toughened hybrid composites through natureinspired hierarchical complexity,

Acta Materialia 2009 57, 29192932.16


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Artificial Nacre the growth

The first successful attempt to replicate nacre, using CaCO3 Mimicking the growth composite, structure, and property:

Calcium carbonate-based nacre in the laboratory by mimicking its naturalgrowth process with layer-by-layer assembly

17 Ullrich Steiner, Nature Communications 2012

Artificial Nacre the growth

Polymer-mediated Mineral Growth:

early-stage crystallization throughsingle PVP pores in a trilayer of

calorg/organic/calorg

Ullrich Steiner, Nature Communications 2012

(scale bar: 500 nm)


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Protein- and peptide-associated biomineralization

Acidic Proteins-mineralization templatesNegatively charged amino acids: particularly glutamate (Glu)

Mechanism:

To recruit and bind inorganic cations, such as calcium, thereby initiating themineralization 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 respectivedistinct CaCO3 crystalmorphologies produced uponincubation of the peptoids with

Ca2+ and sequestered CO2.

Biologically-inducedinorganic materials:

20Chen, C.L. et al., J. Am. Chem. Soc. 2011 133, 52145217.

Biological molecule:

recognition units/domains

nucleation sitesmolecular facets activating crystallizationaid 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 thenegatively-charged glutamic acid

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Natural:

crystalline apatite

Ca10(PO4)6(OH)2

Artificial:

Li, L. et al.,Adv. Mater. 2011, 23, 46954701

Bone Formation

Bone formation: similar hierarchical mineralization of calcium and phosphateions forming hydroxyapatite crystals via collagen matrix

physical properties of collagen Bone morphology & internal organization

22Zhang, 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 andsculptarbitrary 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:

Ba2+ + CO2 + H2OBaCO3 + 2H+

SiO32+2H+SiO2+H2O

By diffusion of CO2 in a solution of BaCl2 and Na2SiO3 Responsive growth of BaCO3-SiO2 structures, toward or away from the bulk solution

Three reaction regimes under two distinct growth modes: continuous anddiscrete modulations, controlled by CO2 concentration, pH, and temperature

Stems SrCO3-SiO2 (pH 11.8)

tulips BaCO3-SiO2 (4oC, pH 11)


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Rational Design

CO2 Flux:

amount direction (orientation of sample)



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) SrCO3-SiO2Stem, (BariumCarbonate) BaCO3-

SiO2 vases.

Rational Design

SrCO3-SiO2 vases containing SrCO3-SiO2 stems (green)

- subsequently opened with a CO2 pulse (blue)

Rhythmical pulsing of CO2 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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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 biogenicroute 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 coatedwith iron oxide, initial product; (b)TMV coated with iron oxide, 6months incubation.

TMV coated with silica; the arrows indicate the lengths of individualviral 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-strandedDNA encapsulated by several coat proteins

30Flynn, 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 biomineralizationtemplates

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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 wasisolated and amplified

concentrated solution of the phage-QD complexes adopts a

liquid crystalline organization -- optical and spectroscopicapplications

32Flynn, C.E. et al., Viruses as vehicles for growth, organization and assembly of materials,Acta Materialia. 2003


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T7 bacteriophage

Sphericalviruses, 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, 4751.33

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 invaried 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, 322327.34


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Microorganisms - diatoms

ZnS:

Diatoms:

Gordon, R. Star Trek replicators and diatom nanotechnology, Trends Biotech. 2003 21, 325328.35

Larger organisms as templates

sea-urchin skeleton - Au replication butterfly-wing microstructures Al2O3using ALD, for photonic applications

Huang, J. et al., Nano Lett. 2006 6, 23252331.Seshadri R. and Meldrum F. C.,Adv. Mater. 2000 12, 11491151.36


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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, primarilyglass 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, bydescribing the roles of organic, inorganic elements and theirinteractions.

Due by 04/08/2014

Hand in hard copy of homework at the TA, Xiying Chen, at thebeginning of the 04/08 class

Please contact [email protected] for questions.

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Lect 11-12 Biomineralization_print

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