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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
2014-04-22
Lecture 21-22
Bioinspired Molecular Machines
What you will learn in the next 60 minutes
Molecular Machines
I. MECHANICAL EFFECTS IN BIOLOGICAL MACHINES
• Skeletal Muscle
• Kinesin
• Rotaxane
II. THEORETICAL CONSIDERATIONS
FLASHING RATCHETS
III. SLIDING MACHINES: rotaxane
– Example 1. Synthetic Molecular Muscle
– Example 2. Shuttle
– Example 3. Walking
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Motion Generation - via Mechanical Machines
Motion:
Coherent change in location of one body with respect to another
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• Macro-scale:
Generated by mechanical machines
• Micro/Nano-scale:
Molecular machines - natural & synthetic
(functional subunits for action with bio-inspired
design)
video
Realizing Controllable Movements – Mimicking & Innovation
• While lift and control are clear
emulations, airplanes do not
propel through the skies like birds.
• “Where biology shows us that
rotary motors and walking
machines are possible, molecular
machinery access to the same
functionality may be realized in
different forms and with different
building blocks.”
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Different types of motion in biology and artificial systems
Leeuwenhoek’s “little animals”
Skeletal muscle’s sarcomere
kinesin
Whitesides’s
autonomous
swimmers
Mallouk’s remote-controlled
catalytic nanorods
Sauvage’s molecular muscles
Stoddart’s nanoelectrochemical system (NEMS)
Stojanovic’s
DNA robot
Leigh’s synthetic walker
I. MECHANICAL EFFECTS IN BIOLOGICAL
MACHINES
• Skeletal Muscle
• Kinesin
• Rotaxane
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1. Skeletal Muscle - Structure and Function
• The contraction and extension of a sarcomere is induced by the
myosin head groups acting on actin filaments.
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video
1. Skeletal Muscle - myosin crossbridge cycle
The movement of myosin motors along actin filaments involves a complex
cycle of :
• nucleotide-binding state, ATP hydrolysis
• changes in conformation, actin affinity
• Pi and ADP disassociation
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Fast response
Highly efficient
ATP binding
‐detachment
energizing
‐attachment
power stroke Pi leaving
www.bms.ed.ac.uk ADP leaving
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2. Kinesin
Kinesin, a motor protein, walks by itself
• utilizing ATP hydrolysis to power its movement
• walks hand-over-hand along a microtubule
• hauling vesicle cargo essential to life’s functions – uni-directionality
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video
ATP/ADP binding and then hydrolysis in the head that is bound to the microtubule allow the unbound head bearing
ADP to take a step forward. The step involves a diffusional search by the unbound head for the adjacent tubulin
unit to settle on to. The front head then releases its ADP, causing it to bind more strongly to the microtubule.
The back head subsequently releases Pi, allowing it to lift off from the microtubule in a sequence that may be gated
by the preceding event. ATP can then bind to the head attached to the microtubule, bringing the motor back to its
initial state.
2. Kinesin
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3. F1-ATP Synthase
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• not coupled to any large-scale work-generating process,
• nor is its biological operation principally driven by ATP hydrolysis
• powered by harnessing a chemical potential created by a pH gradient and using it
to induce rotational motion accompanied by the synthesis of ATP
video
(a) Free ADP binds in empty α/β subunits
(α/βE), forming a complex with them
(α/βDP).
Rotation of the ATPase γ subunit is driven
by H+ transport across a membrane,
permitting the release of synthesized ATP
from the α/βTP subunit.
(b) Surface-mounted ATPase rotates an
actin filament as captured by (c)
fluorescence images.
Common Features of Biological Machines (biomotors)
1. movements: There is clear movement of one component with respect
to another
2. solid supports: The motors and machines are usually interfaced with a
large support material.
3. ATP hydrolyses: Fuel in the form of ATP hydrolysis powers the
movements.
4. binding/debinding Events: Sequential binding and debinding events
are also involved.
5. use of thermal energy: The machines use ambient thermal energy and
Brownian motion to move.
6. chemical cycles: The biomotor performs a cycle of motion that is
intrinsically governed by chemistry.
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II. THEORETICAL CONSIDERATIONS:
FLASHING RATCHETS
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• Directional motion: against accepted law in Chemistry
• In biomotors, the state of the system is different in the forward and backward steps
Change induced in many ways:
• binding,
• ATP hydrolysis,
• redox changes,
• light absorption,
• protonations
cm
Feynman’s thought experiment of a molecular-scale ratchet:
To the left, they get recaptured in the original well when the sawtoothis reinstated. But to the right, they could
progress to the adjacent location once the sawtoothis flashed on again. Thus, “flashing”the potential energy
surface “on”and “off”on appropriate time scales permits limited periods of diffusion, where probability dictates
the particle will most likely maintain its position or move unidirectionallyto the right.
(a) The energy profile of movement in a
CM-scale macroscopic ratchet that
achieves directional movement. (b) a
nanoscaleratchet that does not. (c) A
flashing ratchet along with Brownian
motion circumvents the principle of
microscopic reversibility to drive
movement to the right.
• There are two double-well potentials:
• The stimulus acts on the thermodynamics of the
energy wells by turning states “off” and “on,” a
property known as bistability.
• At the same time, different pathways are switched
“off” and “on” by making the kinetic barriers
larger and smaller, a property defined as bilability.
• Thus, unidirectional motion can be attained
following (1) stimulation, (2) move right, (3)
remove stimulation, (4) move right, and continue
cycling periodically.
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At the molecular level, flat potential surfaces are extremely rare, and so,
unidirectional motion can be achieved by switching between two different
double-well potentials.
• Biomotors operate under similar conditions but greater complexity
• Bioinspired machines – emulating motion at simpler level
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III. SLIDING MACHINES
• Linear Machines: Rotaxanes
• Bistable rotaxanes are elementary machines that display linear motion.
• Composed of ring interlocked around a dumbbell with two stations
The ring’s affinity for one station is
designed to respond to stimulation
by photons, electrons, protons, or other
chemistries, in order to move the ring
controllably from one station to the
other.
When the stimulation is removed,
the ring moves back again. Essentially,
ATP has been replaced with a different
fuel source.
Linear Machines: Rotaxanes
Oxidation and reduction of copper causes the movement of the macrocycle, which is
based on the stereochemical preferences of Cu(I) and Cu(II). The larger macrocycle
translates more rapidly across the dumbbell than the smaller one.
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Example 1. Artificial Muscle
The CBPQT4+ macrocycles to move in/out-ward in this molecular muscle
via oxidation/reduction of the two TTF units
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TTF oxidation-driven movements
rotaxanes are attached to a
cantilever via the disulfide
linker on the CBPQT4+
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Example 2. Artificial Molecular Shuttle
• A typical molecular shuttle design relies on surface-adhered kinesin
motors to transport functionalized microtubules that carry different types
of cargo.
“ Engineering Applications of Biomolecular Motors” H. Hess, Annu. Rev. Biomed. Eng. 2011
Example 3. Synthetic Molecular Transporter DNA motor
and track
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Reading Resources
Natural:
• TEDxSydney - Drew Berry - Astonishing Molecular Machines
http://youtu.be/DfB8vQokr0Q
(Malaria, Mosquito bite, Drew Berry – a biomedical animator whose scientifically
accurate and aesthetically rich visualisations reveal the microscopic world inside our
bodies to a wide range of audiences)
Artificial:
• “Engineering Applications of Biomolecular Motors” H. Hess, Annu. Rev.
Biomed. Eng. 2011
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Summary of the Course
• What are Bioinspired Engineering and Bioinspried Materials?
– Understanding natural biological systems
– Taking their strategy to create/engineer new material (systems)
– Structure – Property -- Functions
• Wide Scales:
System - organism – organ – tissue – cell – proteins - DNA - molecules
• Wide Variety…
shapes?
material/composition?

Biomineralization
Protein templated assembled and
crystalized CaCO
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Why can it walk on water?
What’s the feature on the feet?

Superhydrophobic materials
Common Basilisk
One of the few animal species that can walk on water
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Why this shape?
For beauty?

or sailing.
Velella velella
sea raft, by-the-wind sailor, purple sail
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Signaling?
For prey? communication?

Bioluminescent
light emitting materials
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Iridescent color
From pigment? or structure?

Structuring color
Bio-optics, photonics
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Both self-cleaning surface?

Dynamic self-cleaning
and Drag reduction
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Both Adhesive?
Dry v.s. Under water

Structure
v.s.
Chemistry
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Course Topics
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Topics:
* Stimuli-Responsive Hydrogels
Biomimetic Self-oscillating Polymer gels
Stimuli-Responsive Surfaces in Biomed App
Stimuli-responsive Conjugated Polymers: from electronic noses to
Artificial Muscles
* Artificial Photosynthesis
* Biological geological technic,
* Neural networks and bioinspired computers
* Biomimetic Surfaces I: Adhesion & Wetting
Color-Photonic Materials
Biomimetic Surfaces II: Biosensing
Cell-Surface Interaction
* Biomineralization I: Protein
Biomineralization II: Organism
* Tissue Engineering: Organs
Cell seeding; TE scaffolds
* Self-assembly I: Self-assembled structure
Self-assembly II: Principles of cooperativity in Bioinspired Self-
assembling systems
* Bioinspired Molecular Machines
Bioinspired Materials & Biomaterials
Subject Focus:
1. developing a fundamental understanding of the synthesis, directed self-
assembly and hierarchical organization of natural occurring materials,
2. using this understanding to engineer new bioinspired artificial materials for
diverse applications.
Content:
provide a broad overview of these most recent advances in bio-inspired materials,
covering:
natural materials, biomimetic and bioinspired artificial materials
with an emphasis on:
synthesis, processing, hierarchical design from the nano- to the macro-scale,
properties and characterizations, as well as real-life applications
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At the end of the course
• Better understanding of
– the biologically inspired materials and biomaterials, as well as hybrid
material systems
– fundamental principle of material design
– synthesis and assembly
– characterization of structure, properties and behaviors
• Be inspired to innovate your own new materials
– propose original research topics
– study natural biological systems and select and design materials for
specific applications
– determine processing conditions that leads to materials for specific
applications
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Structure of the Course
Lecture
Homework
Lit Rev
Original
research
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Basic Concepts & knowledge
Broadening up-to-date research
Try your bioinspired idea
Review & deeper understand
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Proposal
Template:
1. Abstract (1 page)
2. Project Description (8-11 for grads, 6-9 for undergrads)
– clearly state your Novelty and Research Plan
3. Summary (1 page)
NEW FORMATTING!
• Font: Arial 11 or Times new Roman 12
• Spacing: 1.5 line
* Changes highlighted in red
Presentations
• Best Proposal Presentation Award (x2)
– A prize for a student with the highest evaluation in each group
– Evaluation Criteria:
 Significance/Impact (5)
 Novelty/Originality (5)
 Feasibility/Practicality (5)
 Structured/Comprehensive (5) – clearly state your Novelty and Research Plan
• Time: 10-minute presentation + 3-minute questions.
• Ready for presentation:
– Please upload your presentations by 11:30 AM on the day of your presentation
(Apr 19 or May 1) to Google Drive. I’ll copy them to the computer in classroom.
– Otherwise, bring your presentation in USB stick and copy it to the computer in
classroom by 1:20 PM on the day of your presentation.