Bionanomaterials: Biological

Building Blocks and

Bionanomaterials
(nanofibers\nanotubes)
Nanotube vs Nanofiber
 Carbon Nanotubes (CNTs)

Carbon Nanotubes (CNTs)

 INTRODUCTION
INTRODUCTION: History
what are
What are they?
they?

• Carbon nanotubes (CNTs) are hexagonally shaped arrangements of

carbon atoms that have been rolled into tubes.
• Diameter: less than 1 nm.
• Length: from a few nanometers up to a millimeter.
• Rolling up a graphene sheet may lead to a CNT (For imagination only!).

Adopted from “http://www.physik.uni-regensburg.de” 3

 INTRODUCTION: History
History

• 1952:
Radushkevich and Lukyanovich showed hollow graphitic carbon fibers
with 50nm diameter.

• 1979
Abrahamson presented evidence of carbon nanotubes at the 14th Biennial
Conference of Carbon at Pennsylvania State University.

• 1981
A group of Soviet scientists published the results of chemical and structural
characterization of carbon nanoparticles produced by a thermocatalytical
disproportionation of carbon monoxide.

• 1991
Nanotubes discovered in the soot of arc discharge at NEC, by Japanese
researcher Sumio Iijima.
5
CNT TypesINTRODUCTION:
INTRODUCTION:CNT
History
types
Based on symmetry

(n,m)

n= column
m= row

If:
n=m  Armchair
n≠m  Chiral
(n,0)  Zig-Zag

6
CNT TypesINTRODUCTION:
INTRODUCTION:CNT
History
types
Based on walls

Single Wall CNT Multiple Wall CNT

or or

Parchment model Russian doll model

7
 PROPERTIES:
INTRODUCTION:
Mechanical
History
Mechanical

Materials Young’modulus(Tpa) Tensile strength(Gpa) Elongation at

• Carbon nanotubes are the strongest, flexible and stiffest mater ials yet
break(%)
discove ed in terms of tensile streng th and elastic modulus res pectively.
SWNT E ~1 (from 1 to 5) 13-53 16
r
• The hardness (152 Gpa) and bulk m odulus (462–546 Gpa) of carbon
Armchair 0.94 126.2 23.1
nanotub es are greater than diamond, which is considered the h ardest material.
SWNTT
• SWNT
Zigzag The current
T Young’s0.94
modulus value of SWCNs94.5
is about 1 terapascal.15.6-17.5

• SWNT
Chiral The mo dulus of the 0.92
multi walled carbon nanotubes correlates to the amount
of disor der in the carbon nanotube w alls.
MWNTE 0.2-0.8-0.95 11-63-150
• when multi walled carbon nanotubes break, the outermost layers break first
Stainless steelE 0.186-0.214 0.38-1.55 15-50

KevlarE 0.06-0.18 3.6-3.8 ~2

EExperimental observation; TTheoretical prediction

7
PROPERTIES
PROPERTIES:
INTRODUCTION:
ElectricalHistory
conductivity
Electrical conductivity

• CNTs can be metallic or semi-conductors due to their geometry.

• For a given (m,n) nanotube:

- If n=m (armchair)  the CNTS is metallic

- If n-m is multiple of 3  the CNTs is semiconducting with a
small band gap.
- Otherwise ,the CNTs is moderate semiconductor.

• In theory, metallic nanotubes can carry an electric current density of

4 × 109 A/cm2, which is more than 1,000 times greater than those of
metals such as copper.

• They are one dimensional conductors only along the axis

9
PROPERTIES
PROPERTIES:
INTRODUCTION:
Thermal History
conductivity
Thermal Conductivity

• SWNTs room-temperature thermal conductivity is about 3500 W/(m·K) and

over 3000 W/(m·K) for individual MWNT.

• Addition of nanotubes to epoxy resin can double the thermal conductivity for a
loading of only 1%, showing that nanotube composite materials may be useful
for thermal management applications.

• All nanotubes are expected to be very good thermal conductors along the tube,
but good insulators laterally to the tube axis.

10
PROPERTIES
PROPERTIES:
INTRODUCTION:
Thermal History
conductivity
Optical

• Flourescence:

 Semiconducting SWCNTs emit and absorb NIR.

 No excitonic luminescence in metallic tubes.
 Photoluminescence is used for measuring the quantities of semiconducting
nanotube species in a sample.
 Also to identify the symmetry and (n,m) properties.

• Raman spectroscopy:

 Raman spectroscopy has provided an exceedingly powerful tool for

characterization of CNT’s with respect to their diameters, and quality of the
samples properties.
 SWCNT and MWCNT can be discriminated via this method.

11
 SYNTHESIS INTRODUCTION:
SYNTHESISHistory
I. Arc discharge method

• The most c ommon and perhaps easiest way to produce CNTs.

• Carbon con tained in the negative electrode sublimates b ecause of the

high-discharge temperatures.

• The yield for this method is up to 30% by weight and it produces both
single- andmulti-walled nanotubes with lengths of up to 50 micrometers
with few st ructural defects.

• Produces a complex mixture of components, and requir es further

purification - to separate the CNTs from the soot and th e residual catalytic
metals pre sent in the crude product.

12
SYNTHESIS INTRODUCTION:
SYNTHESISHistory
II. Chemical vapor deposition (CVD)

• As ubstrate is prepared with a layer of metal catalyst particles, most comm only
nickel, cobalt, iron , or a combination.

• The substrate is heated to approximately 700°C.

• two gases are bled into the reactor: a process gas (such as ammonia , nitrogen or
hydrogen ) and a carbon-containing gas (such as acetylene , ethylene , ethanol or
methane ).

• Nanotubes grow at the sites of the metal catalyst; the carbon-containing g as is broken
apart at the surface of the catalyst particle, and the carbon is transported to the edges
of t he particle, where it forms the nanotubes.

• Attracted attentions for its feasibility and potential for large-area productio n with
reasonable growth rates at relatively low temperatures.
13
SYNTHESIS SYNTHESIS
III. Laser ablation

evelop on the cooler surfaces of the reactor as the va

d surface may be included in the system to collect t

• The laser ablation method yields around 70% and produces prima rily single-
walled carbon nanotubes with a controllable diameter determined by the reaction
temperature .

• However, it is more expensive than either arc discharge or chemic al vapor

deposition.

14
APPLICATION
INTRODUCTION:
APPLICATIONS
History
I. AFM/STM Tips

• More slender tips  higher resolution will gain in microcopy.

• In addition, d ue to the high elasticity of the nanotubes, the tips d o not suffer from
crashes on c ntacti Tip
with the substrates.

• Biological m lecules, such as DNA can also be imaged with hi er resolution using
nanotube tip compared to conventional STM tips.

CNT Probe

Chang et al., Jpn. J. Appl. Sci. 43(7B), 4517-4520 (2004).

Chang et al., Jpn. J. Appl. Phys. 43(7B), 4517-4520 (2004).
15
Tang et al., Nano Lett. 5(1), 11-14 (2005).
APPLICATION
INTRODUCTION:
APPLICATIONS
History
II. Filters/membranes

16
 APPLICATION
INTRODUCTION:
APPLICATIONS
History
III. Molecular carriers

• An important issue in intracellular drug delivery is the poor permeability of

the plasma membrane to many drugs.

• Thus, various carriers, including polyethylene glycol, peptides and lipids,

have been developed to facilitate the cellular entry of drugs.

• Recently, the feasibility of using SWNTs for intracellular drug delivery has
been demonstrated.

• They have high drug loading capacities and good cell penetration
qualities.

• Problems: lack of solubility, clumping occurrences, and half-life

17
APPLICATION
INTRODUCTION:
APPLICATIONS
History
IV. Biomedical imaging

• Semi-conductive SWNTs with appropriate chirality can generate a small

band gap fluorescence of 1 eV, which corresponds to NIR range (900-1600
nm).

• Biological tissues have very low absorption, scattering, and

autofluorescence in this range and therefore, are very useful forbiological
imaging.

• CNTs show great promise in NIR photoluminescence imaging , Raman

imaging and optical absorption agent for photoacoustic imaging.

19
 APPLICATION
INTRODUCTION:
APPLICATIONS
History
V. Bio-sensing

• A biosensor is a bioanalytical
device consisting of 2
components:
a bioreceptor and a transducer.

• The bioreceptor is a
biomolecule that recognizes the
target analyte whereas the
transducer converts the
recognition event into a
measurable signal.

20
 Bio-sensing

• SWNT biosensors can exhibit large changes in electrical impedance and

optical properties in response to the surrounding environment which is
typically modulated by adsorption of a target on the CNT surface.

• Low detection limits and high selectivity require engineering the CNT surface
(e.g., functional groups and coatings).

• CNT plays dual role in a biosensor both as immobilization matrices and as

electron mediator.

21
 APPLICATION
INTRODUCTION:
APPLICATIONS
History
DNA Sequencing

• A biosensor is a bioanalytical
device consisting of 2
components:
a bioreceptor and a transducer.

• The bioreceptor is a
biomolecule that recognizes the
target analyte whereas the
transducer converts the
recognition event into a
measurable signal.

22
 CHALLENGES
• Cost: Too expensive (~ $ 200per gram)

• Toxicity: there are some reports showing CNTs can

damage DNA or causing pulmonery toxicity.

• Manipulation: hard to purify and the ability to

manipulate structures at the atomic scale.

• Large-scale production: Large quantity fabrication

process still missing.

23
 SUMMARY

• CNTs have special properties which makes them interesting

in many fields.

• There is still a great need of improving its production and

manipulation.

• In biotechnological applications, we must care especially

when studying them for biomedical applications.

• Using CNTs for us biotechnologists needs a team work

since a deep knowledge will be gained when working in
interdisciplinary discipline!
24
Carbon Nanotubes (CNTs)

Nanofibers
DEFINITION

Nanofibers are defined as fibers with diameters less than 100

nanometres.

At the right a human hair

(80,000 nanometers) is
place on a mat of
nanofibers

SINGLE
HUMAN HAIR
NANOFIBER
Collagen Fibers
Formed Of Parallel
Fibrils High Modulus Of
Elasticity

1.5 nanometers in diameter

300 nanometers long;

20 collagen types that exist in animal tissue

Assembly Of Collagen Fibers
 Elastin Fibers
• An amorphous protein
• Much lower modulus of
elasticity than collagen
• Primary constituent of
many ligaments
• Crosslinked
tropoelastin
 Elastin Is An
“Entropic Spring”
• ΔG = ΔH – TΔS

• ΔH = enthalpy changes, which don’t normally happen in

solvents.
•
ΔS = entropy
changes… changes in
the degree of order
• Stretching a polymer
increases it’s order,
and makes ΔS
negative.
• ΔG is then positive,
and unfavorable.
NANOFIBERS - INSPIRATION
ECM fibers ~ 50-500 nm in diameter
Cell ~ several-10 um
Fibers 1-2 orders of magnitude < cell
single cell contacts thousands of fibers

three techniques to achieve Nano-fibers scale

- Self Assembly
-Phase Separation
-Electro-spinning
-Polymerization

*Antisolvent-induced polymer precipitation and

electrostatic spinning.Carbon nanofibers are
produced by catalytic synthesis.
 Nanofibers range in diameter of 2-600 nanometers and are very
difficult to see with the naked eye so they are studied using
magnification…
 Much research has been done on spider dragline silks. The
strength of a spider dragline is much stronger than a steel fiber
of equivalent size.

Electron micrograph of nanofibers Spider dragline 3,000

used for tissue scaffolds nanometers
Leaf with
nanofibers
containing
pesticide
UNIQUE PROPERTIES OF NANOFIBERS
 Size: Nanofibers are very small which gives them unique physical and
chemical properties and allows them to be used in very small places.

 Surface-to-volume ratio: Nanofibers have a huge surface area compared to

their volume. So scientists
have lots of surface to work with!
The huge surface area available on a nanofiber makes it very suitable for
new technologies which require smaller and smaller environments for
chemical reactions to occur. Increasing the surface area speeds up a
chemical reaction.
Single Box Ratio
6 m2
= 6 m2/m3
1m 3

Smaller Boxes Ratio

12 m2
= 12 m 2/m3
1 m3
 Techniques To Achieve Nano-fibers For TE

Self-assembly

Phase separation

Electrospinning
NANOFIBERS: SELF-ASSEMBLY
Definition: spontaneous organization into stable structure without
covalent bonds

Biologically relevant processes

- Cellulose,Lipids, DNA, RNA, protein organization
- can achieve small diameter

Example: peptide-amphipathics
- hydrophobic tail
- cysteine residues  disulfide bonds
SELF-ASSEMBLY
• Relies on non-covalent interactions to
achieve spontaneously assembled 3D
structure.
•
Biopolymers such as peptides and nucleic
acids are used. Example is peptide-
•
amphiphile (PA)
•
(A)Chemical structure of (PA)
(B)Molecular model of the PA showing
• the narrow hydrophobic tail to the
bulkier peptide region Nanofiber

(C) Schematic of PA molecules into a peptide-amphiphile

cylindrical micelle.5
 PHASE SEPARATİON
• Definition: thermodynamic separation of polymer solution into
polymer-rich and polymer-poor layers
• This process involves dissolving of a polymer in a
solvent at a high temperature followed by a liquid–
liquid or solid–liquid phase separation induced by
lowering the solution temperature
• Capable of wide range of geometry
s and dimension
include pits, islands, fibers, and irregular pore structures
• Simpler than self-assembly

a) powder, b) scaffolds with continuous network, c) foam with closed pores.4

NANOFIBERS: ELECTROSPINNING
 Definition: An electric field pulls on a droplet of polymer solution at the tip
of the syringe and pulls out a small liquid fiber. It is pulled thinner and
thinner as it approaches the collection plate.

A- polymer solution in syringe

B- metal needle
C- high voltage applied to need
D- electric field overcomes
solution surface tension;
polymer stream generated
E- fibers 1) collected and
2) patterned on plate
ELECTROSPINNING A POLYMER SOLUTION
TO PRODUCE NANOFIBERS

 This picture shows the

actual spinning of a solution
made of the polymer PEO
(polyethylene oxide)
dissolved in water.

 Polymer solutions can be

electrospun because of their
long repeating units.

 The resulting fiber is

collected below on a
grounded plate
 Controllable Parameters:
ELECTROSPINNING •Deposition height
•Too high, no fiber deposition; too low, chance of
arching
•Polymer Concentration
•Too high, viscosity will not allow fiber
formation; too low, globules of polymer will
form
•Voltage Applied
•Too high, chance of arching, too low, not
enough pull to form fibers
•Flow Rate
Figure 1:Experimental ElectrospinningApparatus •Too high, globules form; too low, inconsistent
fiber deposition
•Needle Diameter:
•diameter of nanofibers increase with gauge
•Fiber Alignment

Standardized Parameters for Nanofiber Fabrication with PLGA

(poly lactic-co-glycolic acid) polymer:
•Deposition height: 7cm from needle tip to receiving plate
•Polymer Concentration: 10% PLGA in HFIP(hexafluoro-2-propanol)
•Voltage Applied: 15kV
•Deposition Patterning: Random Deposition (No patterning)
•Flow Rate: 30 µL/Min
Figure 2:Electrospinner
Mechanics •Needle Diameter: 20 gauge
NANOFIBERS: ELECTROSPINNING

- multiple polymers can be combined at

1) monomer level
2) fiber level
3) scaffold level
- control over fiber diameter
alter concentration/viscosity
- fiber length unlimited
- control over scaffold architecture
target plate geometry
target plate rotational speed Current
approaches combined techniques
- usually electrospinning + phase separation
- fibers woven over pores
NANOFIBERS: OVERVIEW
 ELECTROSPINNING POLYMERS
Chemical Synthetics
- Polyglycolic acid (PGA)
- Polylactic acid (PLA)
- PGA-PLA
- Polydioxanone (PDO)
- Polycaprolactone
- PGA-polycaprolactone
- PLA-polycaprolactone
- Polydioxanone-polycaprolactone
Natural
- Elastin
- Gelatin collagen
- Fibrillar collagen
- Collagen
Fibrinogenblends
- Heamoglobine
POLYGLYCOLIC ACID (PGA)
Properties Parameters
- surface area to volume ratio
- Biocompatible *
- consistent mechanical properties
hydrophilic
predictable bioabsorption
- electrospinning yields diameters ~ 200 nm
POLYGLYCOLIC ACID (PGA)

Random fiber collection (L), aligned collection (R)

POLYLACTIC ACID (PLA) – 200 nm
- aliphatic polyester
- L optical isomer used
by-product of L isomer degradation = lactic acid
- methyl group decreases hydrophilicity
- half-life ideal for drug delivery

Parameters (similar to PGA)

- surface area to volume ratio
- spinning orientation affects scaffold elastic modulus

Compare to PGA

- low degradation rate

- less pH change
 POLYLACTIC ACID (PLA) – 200 nm

Thickness controlled by electrospin solvent

Chloroform solvent (L) ~ 10 um, HFP (alcohol) solvent (R) ~ 780 nm

What do you do to combine all properties in one composite?
Both fibers randomly collected
 PGA+PLA = PLGA

- tested composition at 25-75, 50-50, 75-25 ratios

- degradation rate proportional to composition
- hydrophilicity proportional to composition

Recent Study
- delivered PLGA scaffold cardiac tissue in mice
- individual cardiomyocytes at seeding
- full tissue (no scaffold) 35 weeks later
- scaffold loaded with antibiotics for wound healing
POLYDIOXANONE (PDO)
- crystalline (55%)
- degradation rate between PGA/PLA ,close to 40-60 ratio
- shape memory
- modulus – 46 MPa; compare: collagen – 100 Mpa, elastin – 4 MPa

Advantages
- PDO ½ way between collagen/elastin, vascular ECM components
- cardiac tissue replacement (like PLGA)
- thin fibers (180nm)
 POLYCAPROLACTONE (PCL)
- highly elastic
- slow degradation rate (1-2 yrs)
- > 1 um
- similar stress capacity to PDO, higher elasticity

Applications Loaded with:

- collagen cardiac tissue replacement
- calcium carbonate bone tissue strengthening
- growth factors mesenchymal stem cell differentation
POLYCAPROLACTONE + PLA

Clinical Applications
- several planned
- all vasculature tissue
- high PLA tensile strength react (constrict) to sudden pressure
increase
- increased elasticity with PCL passively accommodate large fluid flow
ELASTIN
- highly elastic biosolid (benchmark for PDO)
- hydrophobic
- present in: vascular walls, skin

Synthesis of Biosolid?
- 81 kDa recombinant protein (normal ~ 64 kDa)
- repeated regions were involved in binding
- 300 nm (not as small as PDO ~ 180 nm)
- formed ribbons, not fibers – diameter varies
COLLAGENS: GELATIN
- highly soluble, biodegradable (very rapid)
- current emphasis on increasing lifespan

COLLAGENS: FIBRIL FORMING

Type I
- 100 nm (not consistent)
- almost identical to native collagen (TEM)
- present is most tissues

Type II
- 100-120 nm (consistent)
- found in cartilage
- pore size and fiber diameter easily controlled by dilution
COLLAGENS BLENDS
In context: vasculature
- intima – collagen + elastin
- media – thickest+ elastin+collagen
- adventia – collagen
RECONSTRUCTING THE MEDIA
- SMC seeded into tube
- average fiber ~ 450 nm
slightly larger ECM fibers
- incorporation of GAG
carbohydrate ECM
collagen crosslinker
mediate signalling

- cross section of tube wall

- 5 day culture
complete scaffold
infiltration
 FIBRINOGEN
- smallest diameter (both synthetic and bio) 80,
310, 700 nm fibers possible
- high surface area to volume ratio
increase surface interaction used in
clot formation

Stress capacity comparable to

collagen (80%)
 HEMOGLOBIN
- hemoglobin mats
- clinical applications:
drug delivery
hemostatic bandages
- fiber sizes 2-3 um
- spun with fibrinogen for clotting/healing
- high porosity = high oxygenation
FUNCTIONALIZATION
APPLICATION Nanosensors
-Thermal sensor
-piezoelectric sensor
-Biochemical sensor
Military protection Industrial
clothing -Florescence chemical
sensor
Application
-Minimal impedance to -Micro/nano
air
electronic devices
-Trapping aerosol
-Anti-bio/chemical -LCD devices
gases -Electroststic
dissipation

Nanofibers
APPLICATION
Life Science Application
Cosmetic skin masks
Drug Delivery Carrier
-Skin Cleansing
-Haemostatic Devices
-Skin Therapy
-Wound Dressing
-Skin Healing

Nanofibers
Tissue Engineering
Scaffolds Filtration media
-Membranes for skin
-Liquid filtration
-Tubes for blood vessels
-Gas filtration
-3D Scaffolds for bone
&cartilage regeneration -Molecular filtration
NANOFIBER APPLICATIONS
Drug delivery system:
-Encapsulation of the drug inside the electrospun
fiber
-Improve therapeutic efficacy due to the high surface area
and safety of drugs (Dissolution rate of a particulate drug
increases with increasing surface area of both the drug and
the corresponding carrier if needed.)

Wound dressing:
 Novel polymeric composite materials that have
antimicrobial properties and variable surface properties that
can reduce attachment and adhesion to the wound.
 - Wound dressings having antibacterial properties would
be highly desirable for wounded personnel
 USES OF NANOFIBERS…
 High surface area: Filtration, Protective clothing.
Nano-Tex fabrics with water,cranberry
juice, vegetable oil, and mustard after 30
minutes (left) and wiped off with wet paper
towel(right).

Filter applications: Oil droplet

coalescing on nanofibers
increase .
USES OF NANOFIBERS…
 Structure:Fuel cell, Micro/Nano
electronic devices

Nanofibers can be used to

greatly decrease the size of a
fuel cell while increasing the
electrical output.
ROBO-RATS
 Rat steered by a
computer can find
buried earthquake
victims (or) dispose
off bombs
 Carbon nanofibers
electrodes are
implanted to the
rats brain
 Movements signal
transmitted from a
computer to rat’s
brain.
Protective
Clothing
CHIPS USING DNA TEMPLATES
 Nanofibers are connected to proteins
 A segment of DNA is replaced using the concept of
RECOMBINATION
 DNA is coated with gold on both ends passing electricity
through it simulating a transistor

IT CAN ALSO USE IN….

 Health care - Used in drug delivery systems, tissue
engineering, artificial joints
 Environment - Removal of impurities, filtration, food
processing.
 Electronics - Storage devices, quantum electronics,
sensor applications.
 They also find their applications in lithium-ion batteries
and more.
 ORTHOPEDIC AND NEURAL IMPLANTS
 Nano fibers are compatible with human tissues.
 Can create better bone & neural implants.
 Compatibility arises from similarity in body tissue and Nano
structure.
 Orthopedic Nano implants – Commercially available in 5 – 10
years.

Recently, researchers have found that nanofiber meshes

could be used to fight
against the HIV-1 virus, and be able to be used as a
contraception.
Cell and Tissue Engineering, Nanotechnology

Cells Scaffolds

Tissue
Engineering

Bioreactors Signals
Tissue Engineering (TE)
• Scaffolds
Biomaterials, which may be natural or artificially
derived, providing a platform for cell function, adhesion
and transplantation

• Cells
Any class of cell, such as stem or
mesenchymal cell

• Signals
Proteins and growth factors driving the cellular
functions of interest

• Bioreactor
System that supports a biologically active environment
(ex. Cell culture)

• Robots
• Biomedical devices: Pacemaker, Hemodialysis
• Engineering of tissue
• Tissue hierarchy Image sourse: Stke.sciencemag.org, Nature.com
Hierarchical organization of human systems
Organ
Cells Tissue Organ
System
Concept of Tissue Engineering

CELLS

•CELLS
•Cell culture techniques
Extra
Cellular •ADHESIVE PROTEINS
Matrix •Three dimensional SCAFFOLD
which can mimic natural ECM
(ECM)
Katti, Directions, 2005
Examples of tissue engineering

Heart valve

Urinary Bladder

Artificial Skin
 Cartilage

Brighton CT edt. Clinical orthopaedics and related research, 2001

Microstructure of collagen fiber
 Mimetics of cartilage tissue
Physical mimetics Chemical mimetics Biological mimetics

1. Size 1. Protein
1. Matching
2. Alignment chemical 2. Protein
content delivery
3. Architecture (chitosan and
3. Cell behavior
collagen)
2. Manipulating
chemical
composition
 Physical Mimetics

Shape & Size Architecture

Alignment
mimetics

Synthesis of aligned and Hierarchical

random nanofiber arrangement
by electrospinning of nanofibers
Chemical Mimetics
Matching chemical
Manipulating Surface
content
chemical mimetics
(chitosan and
composition
collagen)

Poly (lactic acid) (PLA) Modification of

Poly(lactide-co-glycolide) surface chemistry
(PLGA)
COOH NH COOH
2
NH2 COOH
NH2

Polymer Blend for Improved

protein affinity

1. PLGA/PLA-PEG
2. PLGA/PEG-PPG-PEG
Surface Energy Measurement

85
Chemical Mimetics
1.Surface Functionality
• Grafting of –COOH group (Hydrolysis)
• NaOH
• Grafting of –NH2 (Aminolysis)
• Ethylenediamine(ED)
• N-Aminoethyl-1,3-propanediamine(AEPDA)

COOH COOH
NH2
NH2
COOH
NH2

PLGA
NaOH treatment of PLGA and quantification of Carboxylic group
0.01N NaOH 1min
0.01N NaOH 5min 0.01N NaOH 10min
Toluidine absorbance assay
Time (min) Carboxyl group
in micromole
Per matrix.
1 0.022865
2 0.021300
3 0.016939
4 0.025046
5 0.028344
6 0.030469
7 0.028120
8 0.038240
9 0.0344943
10 0.0272823
 Ethylenediamine(ED)

0.01 M 1 minute 5 minute 10 minute

N-Aminoethyl-1,3-propanediamine (AEPDA)
Biological Mimetics
• Protein adsorption (Adhesive protein)
• Adhesive capability of nanofibrous scaffold
• Stability and orientation of protein after adsorption
• Protein delivery
• Another approach for delivering proteins during
tissue engineering
• Cell behavior
Release studies of adsorbed protein from
PLGA blended with PEG-PPG-PEG

Protein Release

Amount of BSA released (mg/ml)

16
14
12
1 hr
10
8 hr
8
16 hr
6
4
2
0
PLGA PLGA PLGA PLGA PLGA
pure PPG 0.5 PPG 1% PPG 1.5 PPG 2%
% %

90
 Conclusion

COOH COOH
Cells
NH2
Functional Tissue
NH2
COOH Adhesive Proteins
NH2
NH2
Functionalized Nanofiber
Nanofibrous Scaffold

• Physical, Chemical and Biological mimicking enable various

tissue engineering application.
• Tissue engineering holds the promise to develop powerful
new therapies "biological substitutes" for structural and
functional disorders of human health that have proven
difficult or impossible to address successfully with the
existing tools of medicine.
 REFERENCES
• Shao, Wei, et al. "Carbon Nanotubes for Use in Medicine: Potentials and
Limitations." (2013).
• Ajayan, Pulickel M., and Otto Z. Zhou. "Applications of carbon
nanotubes."Carbon nanotubes. Springer Berlin Heidelberg, 2001. 391-425.
• Balasubramanian, Kannan, and Marko Burghard. "Biosensors based on
carbon nanotubes." Analytical and bioanalytical chemistry 385.3 (2006):
452-468.
• Rutledge and Van Vliet groups at MIT
• Dupont-MIT Alliance
• Popov, Valentin N. "Carbon nanotubes: properties and
application." Materials Science and Engineering: R: Reports 43.3 (2004):
61-102.

92
Objectives
• Evaluate the fiber properties (including structural, mechanical,
thermal) at the molecular level as a function of fiber size

• Understand the origin of transition from bulk-like behavior to

nanomaterial behavior: How small is “nano”?
Approach y
• Constructing the simulation
• Step I: Equilibrium simulation in bulk
using Periodic Boundary Conditions x
• Step II: Increase box size in 2
directions. The system remains z
periodic only in Z-dimension