Prof. Ion TighineanuAcademy of Sciences of Moldova

tiginyanu@asm.md

Advanced training Nano-bioengineering 2011-2012

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 Bottom-up Approaches

Optical and x-ray lithography Layer-by-layer self assembly

E-beam and ion-beam lithography

Molecular self assembly

Scanning probe lithography Direct assembly

Atomic force microscopic lithography

Coating and growth

Material removal and deposition

(Chemical, mechanical, or ultrasonic)

Colloidal aggregation

Printing and imprinting

Nanoscale Devices and Integrated Nanosystems

− 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

A NEMS bacteria sensor Nano Lett., 2006, DOI: 10.1021/nl060275y

Nanochip

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

Nanoscale Devices and Integrated Nanosystems

Nanophotonic Systems

A silicon processor featuring on-chip nanophotonic network – IBM Corp., 2008

− 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

− Fuel cells use hydrogen and air as fuels and produce water as by product

− The technology uses a nanomaterial membrane to produce electricity Schematic of a

fuel cell– Energy solution center Inc.

Fuel Cells

500 W fuel cell –

H2economy.com

Nanoscale Devices and Integrated Nanosystems

Lab on chip gene analysis device – IBN Singapore, 2008

Lab on Chip

Drug Delivery Systems

Targeted drug delivery – ACS Nano 2009, DOI: 10.1021/nn900002m

Impact of nanotechnology on drug delivery systems:− Targeted drug delivery− Improved delivery of poorly water soluble

drugs− Co-delivery of two or more drugs− Imaging of drug delivery sites using imaging

− 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

Information Technology Energy

MedicineConsumer Goods

• Smaller, faster, more energy efficient and powerful computing and other IT-based systems

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

• Foods and beverages−Advanced packaging

materials, sensors, and lab-on-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

• Cancer treatment• Bone treatment• Drug delivery• Appetite control• Drug development• Medical tools• Diagnostic tests• Imaging

Nanotechnology Applications

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 θ 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 θ 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

σ So−σ Sw

=σ owcos θ

θwater

Oil

grain surface

oSσ

wSσ

owσ

cos So S w

ow

Young-Laplace equation

θwater

Oil

grain surface

θwater

Oil

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.

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

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.

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.

The Namib Desert Beetle laden with water droplets

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, andplant 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 Transporthttp://onlinelibrary.wiley.com/doi/10.1002/adfm.201103017/pdf

Engineered textured directional surfaces with asymmetric or periodic structures

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

In Nature, directional surfaces on insect cuticle, animal fur, bird feathers, andplant leaves are composed of dual micro-nanoscale features that tune roughnessand surface energy.

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

Bioinspired Directional Surfaces for Adhesion, Wetting, and Transport

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, 719–734

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.

2) Biological materials utilized in nanotechnology

- Proteins, enzymes, DNA, RNA, peptides etc.

Bone cell on porous silicon – Univ. of Rochester, 2007

Cross-linked enzymes used as catalyst – Univ. of Connecticut, Storrs , 2007

Human cell on PSi

Porous silicon (PSi)

Protein

Enzymes are used as oxidation catalysts

•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 Nanoparticles1.´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 molecule• DNA-nanoparticlecomplexes basedon Au-thiol binding• Nanoparticlelabeling for biochips• Labeling of singlemolecules• Devices, e.g.nanoelectronics.

DNA-nanoparticle complexes

DNA-coated gold nanoparticles (NPs) system that uses larger magnetic microparticles (MMPs) to detect

at tomolar (10-18) concentrations of serum proteins

Nanotechnology and diagnosticsDendrimers

Dendrimers, 1- to 10-nanometerspherical polymers of uniformmolecular weight madefrom branched monomers (Polyimido amine), are provingparticularly adept at providingmultifunctional modularity.

Dendrimers can serve as versatilenanoscale platforms for creatingmultifunctional devices capableof detecting cancer and deliverydrugs.

Huge surface leading to dramatic surface effects

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

Nanoporous Materials behave like quasi-freezed Liquids!

Porous Si

• Luminescent quantum structures• Tunable pore dimensions (2 nm to 10 μm)• 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

Properties of Porous Si useful for Applications

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 nanoheteroepitaxy4. Biotechnology (tissue bonding)5. Biosensors (enzyme immobilization)6. Porous Si as explosive element

Porous Si Smart Dust

Prof. M. SailorUCSDUSA

Porous Silicon

Photonic Crystals in Silicon

PCs realization

AMAT, MPI Halle & Infineon

• 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.

Porous Si as bioactive material

• The ability to culture mammalian cells directly onto PS, coupled with the material’s 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.

• 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 Å) between interacting oxygen or other oxidiser, hydrogen and Si atoms – chemical reaction is fast (gun powder: typical grain size is 1 μm)

• Porous Si is solid: no additional geometrical confinement to increase burning rate is required

Porous Si as explosive element

Structural properties of porous Si most essential for explosive interaction

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

Energy 7.5 kJ/gDuration 500 nsTemperature 7000 ºC

Michael J. Sailor Research GroupChemistry and Biochemistry

Nanostructured “Mother Ships”

for Delivery of Cancer Therapeutics

Nanodevices for In-vivo Detection & Treatment of Cancerous Tumors

Nano-Structured Porous SiliconApplied to Cancer Treatment

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

V.V. Ursaki, I.M. Tiginyanu, O. Volciuc, V. Popa, V.A. Skuratov and H. Morkoç.

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

http://nanotechweb.org/articles/news/6/5/19/1

Radiation hardness evaluatedthrough excitonic luminescence 85 MeV Kr+15 ions130 MeV Xe+23 ions

Energy harvester for implantation applications

sapphire substrate

buffer GaN

AlGaN

GaN

µA

GaN nanocones

FLOW

Ti/Au contact

+ - 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.

Applications:

- Artificial pacemaker

- Implanted biosensors

- Flow transducers

Metal oxides

Gasbio

sensors

Membranes

Flatdisplays

Electronicdevices

Transparentelectrodes

IR filters,heat

mirrors

Magneticmemory

Fuel-cells

Metal oxides for various applications

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

SS

Organic-anorganic nanocomposites

Acad. A. Andriesh et al, Institute of Applied Physics, Academy of Sciences of Moldova

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

29

The images of thin films Eu(TTA)3Phen-SBMA on silicon glass substrate without (a) and under UV

excitationЭлектрохимия. 2011, 47(4), 489–498

””ŞŞtiintiinţţa modernă şi tehnologia au a modernă şi tehnologia au

puterea de a modela lumea puterea de a modela lumea îîn care n care

trăim, trăim, îîn bine sau n bine sau îîn rău”n rău”

Frank WilczekFrank Wilczek, laureat al premiului

Nobel pentru Fizică în 2004