MSE 5351: Current Topics in Nanotechnology

Materials Science and Engineering Department

Artificial Molecular Machines

Ninad Ingle
Outline
Introduction to Molecular Machines

Structure and how they work

Integrating individual molecular machines into a device

Characterization of such devices

Applications
Introduction
Machine?

Molecular Machine:
Precise, Controlled Motion at Molecular level

Drastically reduced amounts of energy to undergo

directed molecular motions: Hence reduced amount
of work is observed
Until Now
First Envisioned by Richard Feynamn in 1959
Earliest examples reported by S. Shinkai and O.
Manabe, Nagasaki University, Japan in 1980

Energy sources used for well defined mechanical

movements within molecular machines:
Chemical,
Electrochemical and
Photochemical
Photochemical Process
Light can function at much higher frequencies

No chemical waste is produced

Dual Capacity: Inducing (writing) and Detecting

(reading) of molecular motions
Basic Motions in Molecular Machines
a.) c.)

b.)

a.) Linear Motion b.) Rotary Motion c.) Scissors

Chemical Structure Linear Motion
M: Electron rich macrocycle
P2+: Ru(II)-bipyridine-based light harvesting unit
A12+: 4,4’-bipyridinium strong primary π-electron accepting
unit
A22+: 3,3’-dimethyl-4,4’-bipyridinium weak secondary π-
electron accepting unit
T: tetraarylmethane

Multicomponent,
6+
bistable rotaxane I
The A12+ and A22+ components act as stations for the
macrocycle M. M encircles the A12+ station in the
starting state and can be switched mechanically
between the A12+ and the A22+ stations upon
electromagnetic stimuli.
It was estimated that ~10% optically excited switching
state energy was used for the ring motion with a
mechanical power generated at ~3x10-17 W/molecule.
These molecules can be driven at a frequency of ~ 1
3
kHz and are stable for at least 10 cycles in solution at
ambient temperature.
Chemical Structure Rotary Motion
Chemical Structure Scissors
Bite angle = 9.20 Bite angle = 58.20

trans configuration cis configuration of

of azobenzene azobenzene
Assembly of Molecular Machines
Why?
Microscopic energy is required to stimulate molecular machines to do
microscopic work

Once organized and assembled in a precise manner, the can efficiently link
motion from nanometer scale to macroscopic scale and achieve complex
functions

Molecular machines have been analyzed in solutions, which limit their

potential for device functionality

Most commonly used approaches include:

Langmuir-Blodgett (LB) films
Single molecular machine in matrix
Self-Assembled Monolayers (SAMs)
Self-Assembled Monolayers (SAMs)
Such molecular assemblies are formed spontaneously
by the immersion of an appropriate substrate into a
solution of the coating molecule

SAMs of bistable[2]rotaxane molecules are thus

formed on Au[111] substrate
 Bistable [2]rotaxanes
based on a dumbbell-
shaped component
incorporating the
tetrathiafulvalene unit
(TTF, green) and 1,5-
dioxynaphthalene ring
system (DNP, red) display
shuttling of a ring-shaped
component, the
tetracationic
cyclobis(paraquat-p-
phenylene) cyclophane
(CBPQT4+, blue)

“Structures and Properties of Self-Assembled Monolayers of Bistable [2]Rotaxanes

on Au (111) Surfaces from Molecular dynamics Simulations Validated with Stable Meta-stable
Experiment“S. S. Jang et. Al.
Characterization of Assembled Molecular
Machines
X-ray Absorption Spectroscopy (XAS) and X-ray
Photoemmission Spectroscopy (XPS) are a couple of
many techniques used for characterization of such as
cyclic voltammetry (CV), Raman Spectroscopy and
Scanning Tunneling Spectroscopy (STM)

In XPS, the photoemission intensity of each element

depends on the depth at which the photoelectron is
emitted and it attenuates exponentially with increased
depth
Here, molecular shuttling was monitored by using XPS to
track nitrogen (N) which is only present in the CBPQT4+
ring which shuttles around TTF and DNP units

The movement of such a molecular machine can be

calculated from:

Where,
IA,Z is XPS intensity for a layer of atoms (A) buried at a distance Z underneath the
film surface. I0A represents the signal intensity obtained from a layer of atoms
located at the film surface, λ(EA) is the photoelectron attenuation length of A,
which is a function of the kinetic energy of the emitted photoelectrons, and θ is
the takeoff angle

“Mechanical Shuttling of Linear Motor-Molecules in Condensed Phases on Solid Substrates” T. J Huang et. al.
The nitrogen intensity is significantly higher in the switched state
(shown in red) as compared with that measured in the starting state
(shown in green)

“Mechanical Shuttling of Linear Motor-Molecules in Condensed Phases on Solid Substrates” T. J Huang et. al.
Applications
Molecular machines have been demonstrated to work
as functional elements in molecular electronics,
NEMS, nanophotonics and nanomedicine.

Artificial molecular machines derived from rotaxanes

have many advantages over biological molecular
motors and other conventional motors
 Comparison between biological molecular motors and
bistable rotaxanes

T. J. Huang, "Recent developments in artificial molecular-machine-based active nanomaterials and nanosystems," MRS Bull. 33, 226-231 (2008)
Nanomedicine
Molecular machines can be used as nanovalves which
are stimulas-activated for controlled drug delivery.

Nanophotonics
It has been shown that molecular machines can be used
as light harvesting systems which are actuated by
sunlight to convert it into electrical energy. This
electrical energy was then utilized as a source of
nanoscale power supply.
Molecular machines have also found applications in
plasmonic switches.
Conclusion
Research in the area or artificial molecular machines has
gained momentum in the recent past to obtained
precisely-tailored structures and functions.

Looking at the potential applications of artificial

molecular machines and their advantages over naturally
present biological motors, the field remains equally
interesting to researchers to overcome the challenges like
unidirectional molecular rotors, fater motions over longer
time, molecular machines with rigid backbone and bio-
compatibility
References
 “Light-driven artificial molecular machines: A Review” Journal of
Nanophotonics, Vol. 4, 042501 (25 August 2010)

 V. Balzani, A. Credi, F. M. Raymo, and J. F. Stoddart, "Artificial

molecular machines," Angew. Chem. Int. Ed 39, 3349-3391 (2000)
Thank You!
Questions?