Advanced training Nano-bioengineering 2011-2012

Prof. Ion Tighineanu Academy of Sciences of Moldova tiginyanu@asm.md

Cuprins
1. Nanoscale-size-related phenomena 1. Wettability for cleaning, transport or water collection 1. Design and creation of bioinspired surfaces 1. Synthetic nanomaterials utilized in biomedicine nanoparticles, polymers, porous materials, carbon nanotubes. Dendrimers

 Realization of miniaturized devices and systems while providing more functionality Attainment of high surface area to volume ratio Manifestation of novel phenomena and properties, including changes in: - Physical Properties (e.g. melting point) - Chemical Properties (e.g. reactivity) - Electrical Properties (e.g. conductivity) - Mechanical Properties (e.g. strength) - Optical Properties (e.g. light emission)

Early Plasmonic Nanotechnology

The Lycurgus Cup

Late Roman, 4th century, Probably made in Rome (British Museum)

Stained glass: Notre Dame Cathedral Paris

Stained glass in medieval churches, glazes in ancient pottery were made with... plasmons

Nanoscale Processes and Fabrication

Top-down Approaches
Optical and x-ray lithography E-beam and ion-beam lithography Scanning probe lithography Atomic force microscopic lithography Material removal and deposition (Chemical, mechanical, or ultrasonic) Printing and imprinting

Bottom-up Approaches
Layer-by-layer self assembly Molecular self assembly Direct assembly Coating and growth Colloidal aggregation

Nanoscale Devices and Integrated Nanosystems

Nanochip
Currently available microprocessors use resolutions as small as 32 nm Houses up to a billion transistors in a single chip MEMS based nanochips have future capability of 2 nm cell leading to 1TB memory per chip

Nanoelectromechanical System (NEMS) Sensors

A MEMS based nanochip

Nanochip

Inc., 2006

NEMS technology enables creation of ultra small and highly sensitive sensors for various applications The NEMS force sensor shown in the figure is applicable in pathogenic bacteria detection

A NEMS bacteria sensor Nano Lett., 2006,

DOI: 10.1021/nl060275y

Nanoscale Devices and Integrated Nanosystems

Nanophotonic Systems
Nanophotonic systems work with light signals vs. electrical signals in electronic systems Enable parallel processing that means higher computing capability in a smaller chip Enable realization of optical systems on semiconductor chip

A silicon processor featuring on-chip

nanophotonic network IBM Corp., 2008

Fuel Cells
Fuel cells use hydrogen and air as fuels and produce water as by product The technology uses a nanomaterial Schematic of a membrane to produce electricity fuel cell 500 W fuel cell

Energy solution center Inc. H2economy.com

Nanoscale Devices and Integrated Nanosystems

Lab on Chip
A lab on chip integrates one or more laboratory operation on a single chip Provides fast result and easy operation Applications: Biochemical analysis (DNA/protein/cell analysis) and bio-defense

Lab on chip gene analysis device

Singapore, 2008

IBN

Drug Delivery Systems

Impact of nanotechnology on drug delivery systems: Targeted drug delivery Improved delivery of poorly water soluble drugs Targeted drug Co-delivery of two or more drugs delivery Imaging of drug delivery sites using imaging ACS Nano 2009, DOI:
10.1021/nn900002m

Nanotechnology Applications
Information Technology
Smaller, faster, more energy efficient and powerful computing and other IT-based systems

Energy
More efficient and cost effective technologies for energy production
Solar cells Fuel cells Batteries Bio fuels

Consumer Goods Medicine

Cancer treatment Bone treatment Drug delivery Appetite control Drug development Medical tools Diagnostic tests Imaging Foods and beverages
Advanced packaging materials, sensors, and labon-chips for food quality testing

Appliances and textiles

Stain proof, water proof and wrinkle free textiles

Household and cosmetics

Self-cleaning and scratch free products, paints, and better cosmetics

Medical Nanotechnology or Nanomedicine

Nanomedicine is the application of nanotechnology in medicine, including to cure diseases and repair damaged tissues such as bone, muscle, and nerve Key Goals for Nanomedicine
To develop cure for traditionally incurable diseases (e.g. cancer) through the utilization of nanotechnology To provide more effective cure with fewer side effects by means of targeted drug delivery systems

Wettability is defined as the tendency of one fluid to spread on or adhere to a solid surface in the presence of other immiscible fluids.
Small drops of three liquids - mercury, oil, and water - are placed on a clean glass plate. It is noted that the mercury retains a spherical shape, the oil droplet develops an approximately hemispherical shape, but the water tends to spread over the glass surface.

The tendency of a liquid to spread over the surface of a solid is an indication of the wetting characteristics of the liquid for the solid. This spreading tendency can be expressed in a convenient way by measuring the angle of contact at the liquid-solid surface. The contact angle is considered as

a measure of wettability.

As the contact angle decreases, the wetting characteristics of the liquid increase. Complete wettability would be evidenced by a zero contact angle, and complete nonwetting would be evidenced by a contact angle of 180. There have been various definitions of intermediate wettability but, in much of the published literature, contact angles of 60 to 90 will tend to repel the liquid.

Interface energy:
If matter A and B are brought in contact, there is always a bond formation (at least van der Waals, materials could be also gas and liquid). The lowering of the potential energy that occurs during the interface formation, or the other way round, the energy that is needed to separate the two surfaces is called interface energy. Formation of a crack along the AB interface requires to overcome the interface energy by breaking the bonds. The energy between a solid or a liquid and a gas is often called surface energy.

In 1805, Thomas Young defined the contact angle by analyzing the forces acting on a fluid droplet resting on a solid surface surrounded by a gas

where

= Interfacial tension between the solid and gas = Interfacial tension between the solid and liquid = Interfacial tension between the liquid and gas

Interfacial tension is the work required to create a unit area of new surface

Oil

ow

So

water grain surface

Sw

S S = ow cos
o w

So Sw cos ow

Young-Laplace equation

Oil

Oil

water grain surface

water

grain surface

Water wet

Oil wet

Dynamic contact angle experiments

Sliding Droplet: When a droplet is attached to a solid surface and the solid surface is tilted little by little, the droplet will lunge forward and finally slide downward. The angles formed in the fore and the rear of the droplet lunging forward are respectively called the Advancing Angle and the Receding Angle. The tilting angle of a solid surface when the droplet starts sliding downward is called the Sliding Angle (t).

Superhydrophobicity and superhydrophilicity applied with capillaries

The wetting of a hydrophilic surface gives rise to an increase of the water level in a narrow tube, as there is an energy gain by wetting the surface. A force opposing this is finally gravity, limiting the height that can be reached. On the other hand, on a hydrophobic surface of a capillary, it is possible to press the water out. These effects give rise to superhydrophobic and superhydrophilic surfaces.

Lotus effect: Selfcleaning of biological surfaces

When a droplet of water lands on the lotus leaf, it beads up, rolls off the leaf surface without leaving a trace of water behind and washes away any dirt along its way. This self-cleaning property fascinated scientists for a long time until recently, when scientists realized that this peculiar behaviour is due to the nanostructures present on the surface of the lotus leaf.

1. (Rain) Droplet falls on a surface 2. It forms a spherical surface. 3. It rolls over the surface even only very slightly tilted or from the momentum from falling. 4. The dropplet collects dust. 5. The droplet falls from the leave.

Water striders use surface tension to walk on the surface of a pond Superhydrophobic setae on the tarsi keep the insect afloat while an apical superhydrophilic claw penetrates the surface, allowing it to "grip" the water. The surface of the water behaves like an elastic film: the insect's feet cause indentations in the water's surface, increasing its surface area. This represents an increase in potential energy through the surface tension of the water equal to the loss of potential energy of the insect's lowered center of mass.

www.nature.com/nature/journal/v432/n7013/full/432036a.html

The Namib Desert Beetle laden with water droplets

As the early morning fog drifts across the Namib Desert of south-west Africa, an army of spindly-legged beetles emerges from the sand. Accustomed to an average annual rainfall of one inch, these critters are eager to employ their water collection apparatus that makes them so unique. The process begins when heat is radiated from the matte black exoskeleton, resulting in a body temperature slightly lower than that of the surrounding air. With the beetle's body held at a 45 angle to the sand, the moist breeze contacts the cool exoskeleton and water condenses into small droplets. This beading effect is facilitated by a series of hydrophilic (water attracting) bumps surrounding by a waxy, hydrophobic (water repelling) surface on the insect's back. The droplets may grow to nearly a quarter of an inch, and then roll down to be gratefully sequestered by the beetle's mouthparts. And then it's back down the dunes and away from the morning sun for these diminutive hydroplants.

http://renaturalist.blogspot.com/2011/03/namib-desert-beetle-recipe-for-water.html

Bio-Inspired Materials Nanocomposites

 Structure + Multifunction Surface area and interfaces 104 increase

Fundamentally alter polymer Small vol % huge impacts on properties

Strategy:
Design morphology and interphase Develop hybrid composites

In Nature, directional surfaces on insect cuticle, animal fur, bird feathers, and plant leaves are composed of dual micro-nanoscale features that tune roughness and surface energy. Novel approaches for the design, synthesis, and characterization of new bioinspired surfaces demonstrating unidirectional surface have been demonstrated. The experimental approaches focus on bottom-up and top-down synthesis methods of unidirectional micro- and nanoscale fi lms to explore and characterize their anomalous features. The theoretical component focuses on computational tools to predict the physicochemical properties of unidirectional surfaces.

Bioinspired Directional Surfaces for Adhesion, Wetting, and Transport http://onlinelibrary.wiley.com/doi/10.1002/adfm.201103017/pdf

Engineered textured directional surfaces with asymmetric or periodic structures

In Nature, directional surfaces on insect cuticle, animal fur, bird feathers, and plant leaves are composed of dual micro-nanoscale features that tune roughness and surface energy. http://onlinelibrary.wiley.com/doi/10.1002/adfm.201103017/pdf

Bioinspired Directional Surfaces for Adhesion, Wetting, and Transport

http://onlinelibrary.wiley.com/doi/10.1002/adfm.201103017/pdf

Applications of bio-inspired special wettability. The summarized topics include three areas, the surfaces of superhydrophobicity, surfaces of patterned wettability and integrated multifunctional surfaces and devices. http://mipd.snu.ac.kr/upload/pnt11_2_1/bio_inspired_wettable_surfaces_and_patterned_wettability_ %28advmat_2011_23_719%29.pdf

Super-amphiphobic textiles

Advanced Materials, 2011, 23, 719734

Bioinspired functional living materials by incorporating microorganisms into polymer layers

http://www.pnas.org/content/109/1/90.figures-only

Synthetic materials used in medicine. Dendrimers

Nanoscale Materials
Bionanomaterials 1) Synthetic nanomaterials utilized in biomedical applications
- Polymers, porous silicon, carbon nanotubes, nanodots, nanowires, nanomembranes etc.
Protein

2) Biological materials utilized in nanotechnology - Proteins, enzymes, DNA, RNA,

peptides etc.
Enzymes are used as oxidation catalysts

Cross-linked enzymes used as catalyst Univ.

of Connecticut, Storrs , 2007

Porous silicon (PSi)

Human cell on PSi

Bone cell on porous silicon

Univ. of Rochester, 2007

 The aim of nano-scientists is to virtually imitate nature. They are trying to construct objects out of their most basic components, atom by atom, the way that nature does. This offers an unprecedented degree of precision and control over the final product.

Equipment for Nanoparticles

1.Homogenizer 2. Ultra Sonicator 3. Mills 4. Spray Milling 5. Supercritical Fluid Technology 6. Electrospray 7. Ultracentrifugation 8. Nanofiltration

Homogenizer & Ultra Sonicator

M S Ramaiah Institute of Technology, Bangalore

DNA-nanoparticle complexes
DNA molecule DNA-nanoparticle complexes based on Au-thiol binding Nanoparticle labeling for biochips Labeling of single molecules Devices, e.g. nanoelectronics.

DNA-coated gold nanoparticles (NPs) system that uses larger magnetic microparticles (MMPs) to detect at tomolar (10-18) concentrations of serum proteins

Nanotechnology and diagnostics Dendrimers

Dendrimers, 1- to 10-nanometer spherical polymers of uniform molecular weight made from branched monomers (Poly imido amine), are proving particularly adept at providing multifunctional modularity.

Dendrimers can serve as versatile nanoscale platforms for creating multifunctional devices capable of detecting cancer and delivery drugs.

Huge surface leading to dramatic surface effects

Surface vibrations Surface engineering Quantum size phenomena (antidot, antiwire) Canham, 1990 Good luminescence is indicative of defect-free material and well passivated surface

Nanoporous Materials behave like quasi-freezed Liquids!

Porous Si
Properties of Porous Si useful for Applications Luminescent quantum structures Tunable pore dimensions (2 nm to 10 m) Compatible with Si fabrication technologies, easily patterned High surface area (200 m2/g or up to 103 m3/cm2) Electrically addressable Convenient fabrication of 1, 2, 2.5D optical structures

Porous Si as electronic material

1. Light emitting diodes (1 % external quantum efficiency) 2. Waveguides (tunability of refractive index) 3. Optical memory 4. Photonic bandgap structures (Photonic Crystals) 5. All optical switching (highly nonlinear optical properties) 6. Antireflection coatings (low refractive index) 1. Gas sensing (environmental monitoring) 2. Microelectronics micro-capacitor (high specific surface area) 3. Buffer layer in nanoheteroepitaxy 4. Biotechnology (tissue bonding) 5. Biosensors (enzyme immobilization) 6. Porous Si as explosive element

Porous Si Smart Dust

Prof. M. Sailor UCSD USA

Porous Silicon Photonic Crystals in Silicon

PCs realization

AMAT, MPI Halle & Infineon

Porous Si as bioactive material An effective biomaterial must bond to living tissue - in other words, it has to be bioactive. The success of any medical implant depends on the behavior of cells in the vicinity of the interface between the host and the biomaterial used in the device. All biomaterials have morphological, chemical and electrical surface characteristics that influence the response of cells to the implant. The initial event is the adsorption of a layer of protein on to the biomaterial.

 The ability to culture mammalian cells directly onto PS, coupled with the materials lack of toxicity, offers exciting possibilities for the future of biologically interfaced sensing. This could involve the development of biologically interfaced neural networks, or electronic sensing with signals being directly sent from a living system to a PS device. In this way, porous silicon has the potential to produce devices for replacing damaged tissues in the ear, eye, skin or nasal cavity. Such devices could, for example, receive optical information and convert this to a biological signal that would be passed into neural tissue as a substitute sight sensation.

Porous Si as explosive element

Structural properties of porous Si most essential for explosive interaction
1 cm3 of porous Si contains up to 1000 m2 of internal surface About 20 % of the Si atoms are located at the surface of nanocrystals All surface is covered by monolayer of hydrogen ~ 1022 cm-3 (buffer layer) Contact on the atomic scale (~ 2 ) between interacting oxygen or other oxidiser, hydrogen and Si atoms chemical reaction is fast (gun powder: typical grain size is 1 m) Porous Si is solid: no additional geometrical confinement to increase burning rate is required

Kovalev et al, Phys. Rev. Lett. 87, 68301 (2001).

Energy 7.5 kJ/g Duration 500 ns Temperature 7000 C

Nano-Structured Porous Silicon Applied to Cancer Treatment

Nanodevices for In-vivo Detection & Treatment of Cancerous Tumors

Nanostructured Mother Ships for Delivery of Cancer Therapeutics

Michael J. Sailor Research Group Chemistry and Biochemistry

The Intersection of Solid State and Biological Information Systems

Snail neuron grown on a CMOS chip with 128x128 Transistors. The electrical activity of the neuron is recorded by the chip. (Chip fabricated by Infineon Technologies)
www.biochem.mpg.de/en/research/rd/fromherz/publications/03eve/index.html

Radiation hardness evaluated through excitonic luminescence 85 MeV Kr+15 ions 130 MeV Xe+23 ions

http://nanotechweb.org/articles/news/6/5/19/1 V.V. Ursaki, I.M. Tiginyanu, O. Volciuc, V. Popa, V.A. Skuratov and H. Morko.

Applied Physics Letters, Vol. 90, 161908 (2007).

Energy harvester for implantation applications

FLOW

Tangential flow lead to mechanical deformation of nanocones that will generate piezoelectricity at the base. Charge separation is made by means of an AlGaN/GaN heterostructure.

GaN nanocones

Ti/Au contact

GaN

AlGaN buffer GaN sapphire substrate

Applications:
- Artificial pacemaker - Implanted biosensors - Flow transducers

Metal oxides for various applications

Magnetic memory Transparent electrodes

IR filters, heat mirrors

Electronic devices

Metal oxides

Fuelcells

Flat displays

Gas bio sensors

Membranes

Generating electricity through the deformation of a semiconducting and piezoelectric nanowire

Materials Today, Vol. 10, no 5, p. 20-28 (2007)

NATURE NANOTECHNOLOGY | VOL 5 | MAY 2010 366-373

Organic-anorganic nanocomposites
Acad. A. Andriesh et al, Institute of Applied Physics, Academy of Sciences of Moldova

. 2011, 47(4), 489498

T he images of thin films Eu(T T A)3P hen-SBMA on silic on glass substrate w ithout (a) and under UV 29 exc itation

Eu(TTA)3 Phen-SBMA nanocomposite before (left) and after (right) excitation with UV radiation

tiina modern i tehnologia au puterea de a modela lumea n care trim, n bine sau n ru Frank Wilczek, Wilczek laureat al premiului Nobel pentru Fizic n 2004