4/2/2012

1
Jorge M. Seminario
Department of Chemical Engineering
Department of Material Science
Department of Electrical and Computer Engineering
seminario@tamu.edu
http://che.tamu.edu/seminario
Nanotecnologa
antibody
Nanotecnologa
Unapuerta alfuturo?
Nanoautomvilhechodeunasolamolcula
2
Definicin
3
Nanotechnology is the understanding and control of matter
at dimensions of roughly 1 to 100 nanometers, where
unique phenomena enable novel applications.
Encompassing nanoscale science, engineering and
technology, nanotechnology involves imaging, measuring,
modeling, and manipulating matter at this length scale.
National Nanotechnology Initiative, 2007
http://www.nano.gov
Descubrimientoycontroldela
materiaendimensiones1100
nanmetros
Definiciones
4
Unnanocable desilica envuelveunrayodeluzalrededorde
uncabellohumano(elespesordelnanocable esunmilsimo
delespesordelcabello)
4/2/2012
2
5
http://www.nano.gov/html/facts/The_scale_of_things.html
Notannuevo
6
Ventanasdeiglesiasmedievalesyausabannanopartculas deorodedistintostamaos
paralograrefectosdecolor
Thereisplentyofroomatthebottom*
7
Dr.RichardP.Feynman
Whycannotwewrite
theentire24volumesof
theEncyclopedia
Britannicaonthehead
ofapin?
Dr.RichardFeynman,
oneofAmericasmost
notablephysicists,1918
1988.
http://en.wikipedia.org/wiki/Image:Feynman_an
d_Oppenheimer_at_Los_Alamos.jpg
December12,1959
*Secreequeestafrasela
aprendidelos
microbuseros deLima
manipulacindetomosymolculas
8
SurelyYoureJoking
Mr.Feynman!
AdventuresofaCurious
Character
ByRichardFeynman
Dr.Feynman,Continued
Theproblemsofchemistry
andbiologycanbegreatly
helpedifourabilitytosee
whatwearedoing,andto
dothingsonanatomiclevel,
isultimatelydeveloped a
developmentwhichIthink
cannotbeavoided.
4/2/2012
3
interaccionesdefinidas
porlamecnicacuntica
9
AtomicScale
Acomputerimageof
the selfassemblyof
nano icedoublehelix.
Inthenano iceimage,
oxygenatomsareblue
intheinnerhelix,purple
intheouterhelix.
Hydrogenatomsare
white.
atomsbindingunder
highpressurewithweak
hydrogenlinks
http://ucommxsrv1.unl.edu/unlnews2004/downloadables/photo/20061211helix.jpg
Nuevosinstrumentosdemedicin
10
Scanningprobemicroscope
systemsfromnanoscience
instruments.
Scanningtunnelingmicroscope
(STM)image.
Left http://www.nanoscience.com/products/index.html.
Right http://www.nano.gov/html/facts/home_facts.html.
buckyball(C
60
),pelotadeftbol
11
Buckyballs:HaroldKroto fromthe
UniversityofSussex,RobertCurl
andRichardSmalleyfromRice
Universitywereawardedthe
NobelPrizeinChemistry in1996
fortheirdiscoveryofanew
compositionofcarbon,Carbon60.
12pentagonsand20hexagons
12
4/2/2012
4
bottomupapproach
13
Anexampleofamolecularselfassemblythroughhydrogenbonds
SelfAssembly
Theholygrailofnanotechnology
Manufacturingatombyatom
ThreeTypes
Electrostatic;Capillary;Magnetic
ExamplesinNature
CellularBiology
DNAReplication
Viruses
14
ElectroSelfAssembly
15 16
4/2/2012
5
17 18
19
Nanotubes
Profile
Knownascarbonnanotubesornanowires(noncarbon)
Cylindricalwallwithatomsarrangedinhexagonalorpentagonalfaces
Strengthandstrain
Propertiesofconductors,semiconductorsorinsulators
Highthermalconductivity
Dimensions: from0.4nmindiameter
20
4/2/2012
6
100timesstrongerthansteelatonesixthoftheweight
Tensilestrength:200GigaPascal
Stiffasdiamond Youngsmodulusover1TeraPascal
Multiwallednanotubes
Reinforcedcomposites transportationindustry?Aerospace?
CarbonNanotubes
21
Nanofilter
Filterthesmallestparticles.
NanosizedAluminafibermesh
Waterfiltration
AirFiltration
Sterilization
22
m
e
t
a
m
a
t
e
r
i
a
l
e
s
23
Nanoengranages
24
podranreemplazaralgunosprocesosdefabricacin
4/2/2012
7
Nanorobotsenmedicina
25
Hacia elfuturo
26
Nanotecnologaesomnipresente.Esunrea
emergenteentodaslasramasdelaciencia,
ingeniera,ytecnologa.
Bi enveni dos al
NanoMundo!
Imgenes SEMyTEM
27 28
Quantum
Mechanics
Molecular
Dynamics
Kinetic
Monte
Carlo
Time
Length
Longtimescales:Real
reactiontimes
Reactionmechanism
Shorttimescales
Detailedevolutionof
thesurface
1
st
partof
thistalk
2
nd
partof
thistalk
4/2/2012
8
Quiralidad delosNanotubos
Rollingagraphenelatticeatdifferentanglescancreateavisibletwistin
thecylindricalnanotubestructure
C
H
I
R
A
L

A
N
G
L
E
helical
armchair
zigzag
GrapheneSheet
CHIRALITY PROPERTIES
RandomDistribution
semiconductor
metallic
29 30
ThebiggestChallengeoftheCentury
32
Analizar, disear, y simular materiales, dispositivos y
sistemas electrnicos con detalles (minimum features)
atomsticos (a nivel de nanmetros o nm)
La electrnica tradicional de semiconductores, basada
en silicio esta ya a nivel de nm, pero aun en casos
singulares; el detalle mnimo es de ~30 nm y un
dispositivo (transistor) es de ~0.4 micrometros (m)
Que es la moletrnica?
4/2/2012
9
33
Adems de hacer el anlisis y diseo de
materiales y dispositivos usando
supercomputadoras
Experimentos in silicon: simulacin de
materiales, dispositivos, y sistemas
Simulaciones a Multi-escala:
Nanoscpico (Microscpico)
Mesoscpico
Macroscpico
Que herramientas se usan?
34
La teora esta basada en
1) La fsica atmica/molecular,
2) La qumica quntica,
3) La fsica de estado solido,
4) Ingenieras de materiales, dispositivos, y
sistemas
Que fundamentos/principios?
35
Empezar con mtodos tericos/computacionales y
complementar con experimentos que demuestren
conceptos antes de fabricar; o sea, antes que nada:
Desarrollar la ciencia bsica e infraestructura humana
Pasar progresivamente a la ciencia aplicada; ciencia
que permita la eliminacin de la pobreza e incremente
nuestro nivel de vida, cultura
Invertir en la investigacin hacia metas productivas y
de beneficio para todos; que sea una actividad global
mas que algo de elite y dependiente de donaciones
Como empezar la investigacin?
36
Una de las herramientas fundamentales en el desarrollo
tecnolgico es la supercomputadora
Una supercomputadora, es un clster de computadoras,
econmicas
Computadoras afectan y aceleran el progreso de cualquier
rea de ciencia y tecnologa
Aun la ms veloz es de Japn: la computadora-K opera a
10.51 petaflops (10
15
) con 68,000 procesadores de 8 cores
cada uno (2 GHz) 14/Nov/2011
Punto Importante
4/2/2012
10
37
A C
PEM
(A) Anodo: 2H
2
4H
+
+ 4e
-
(C) Ctodo: O
2
+ 4H
+
+ 4e
-
2H
2
O
Catalizador: Platino
Reducir metal
Nuevo catalizador
Proton Exchange Membrane:
Nafion
Alto flujo de iones
Bajo flujo de electrones
Estable
Nuevo diseo de electrodos
Al
2
O
3
and Ru-Pt
Nano Let t . 2010, 10,
30473051
NVT200 ns
polymeric
H
+
graphite
sheets
Balbuena, et al.
Phys. Chem. Phys.,
12, 27402743
(2010)
Fuel Cells and Solar Energy
Catalyst: Platinum
Cluster
QM
Cytotoxics
Quantum dots
Functionalized CNT
CNT unzipping
MD
Antibody design
Immunoconjugated CNT:
stability and target
membrane infiltration
Genip
Charge transport cytotoxic
& CNT
Charge transport antigen-
antibody
FUERZA
( ) ( ( ) ( ) ( ) ( ))
L M R M
T E Trace EG E EG E
+
= I I
f
f
E V/2
E V/2
2e
I(V) T(E, V)dE
h
+

= A
}
Nanobiotechnology: Drug Delivery System:
quantum dot -antibody
GreensFunctions &DFT
Recognition
Protein-protein
interaction
HER2
Cancer Cell Membrane
Herceptin
Quantum
dots
Iron quantum dot core
could be guided under
magnetic field and impulse
and control the movement
of the drug delivery system
CNT properties:
Adsorbed energy in near IR is converted to heat
Excellent thermal conductivity
Enhanced solubility by functionalization
Chemical inertness
Encapsulate polar and no-polar drugs
Absorb and emit light (good for imaging)
CNT
Bloodstream
pH 7.35
Repulsion
with charged
species
Protonated
groups
Inside cancer cell
Lysosome pH 4.6
+
+
+
+
Recognition
Protein-protein
interaction HER2
Cancer Cell Membrane
CNT vehicle
Computed guided bifunctional scFv Herceptin and
Pertuzumab to Fc from IgG2a
Fab
Fc
Dual pH/Temp sensitive caps
Cancer cell
pH 6.5
Near IR
Infiltrating Malignant Cells with Cytotoxics Concealed in Nanotubes Targeted
for Specific Cancer Therapy. A Theoretical-Experimental approach
Floxuridine
4/2/2012
11
41
Molecular Vessels
Vibronics
Current
Voltage
Molecular
Potentials
Agent
Sensing
Communications
Control
If the agents are molecules, the best detector is another molecule
Hayriesgosparalasalud?
Siendolasnanopartculas msreactivas
debidoasutamao,puedenminimizarla
cantidadrequerida.
Lacontrapartidaesquelareactividad
tambinpuedeactuaranivelcelular(todava
losriesgosnoseconocenmuybien)
43 44
Reducethe
useofPt
Reducethe
useofPt
Ptalloys
Improve
Activity&
Stability
Improve
Activity&
Stability
CoreshellPtalloys
Stabilityagainst
dissolution
Dynamic
evolutionofthe
surface
Stabilityagainst
dissolution
Dynamic
evolutionofthe
surface
Bettercatalysts
Core
Shell
~2.5nm
4/2/2012
12
Significant
contributions to
dentistry
Adhesively bonded
composites conserve
sound tooth structure
for tooth
reinforcement
Provides
cosmetically
acceptable
restoration
Orthodontic Innovations
An Application of Nanotechnology in
Advanced Dental Materials
46
Nano and Molecular Electronics Group
Minicurso de Nanotecnologa
a) Introduccin a la ingeniera de
nanomateriales
b) Ingenieria molecular para electrnica
c) Ingenieria de nanosensores y dispositivos
d) Nanomaterials en ciencia, ingeniera,
biologa, medicina
47
Nano and Molecular Electronics Group
Minicurso de Nanotecnologa
a) Introduccin a la ingeniera de
nanomateriales
b) Ingenieria molecular para electrnica
c) Ingenieria de nanosensores y dispositivos
d) Nanomaterials en ciencia, ingeniera, biologa, medicina
Corriente
Voltaje
Vibracion
es
Potencial
Molecular
Agentes
Qumicos&
Biolgicos
Comunicacion &Control
Amplificadores
CNTs
DNA
Cluster
Caractersticas
Grafeno
Dispositivos
Lgicos
Substratos
Switches
Estadosexcitados
Nanomicro
Interface
CeldasSolares
Sensores
Electrnica
Orgnica
PostCMOS
Electrnica
Molecular
Medicina
Catlisis
NanoMecnico
4/2/2012
13
Enfoquetericoexperimental
Modelamiento
Molecular
Pruebade
Conceptos
Experimentos
Motivacin
Molculas:pequeas,rpidas,ymaseficientes
Grafeno:SuperficiePlasmnica
LUMO 2.91eV HOMO 4.65eV
Densidad
electrnica
total
51
1 flops = una operacin de punto flotante por segundo
1,000,000 = million = 10
6
= 1 megaflops
1,000,000,000 = billion = 10
9
= 1 gigaflops
1,000,000,000,000 = trillion = 10
12
= 1 teraflops
1,000,000,000,000,000 = quatrillion 10
15
= petaflops
1,000,000,000,000,000,000 = quintillion = 10
18
= exaflops
sextillion, heptillion, octillion, nonillion, decillion,.............
A Supercomputer consumes
4-6 MW (5000 homes)
583 racks for exaflops, 67 MW,
160 million cores
UIUC + NCSA+IBM+GLCPC
BlueWaters 10 petaflops
15 MW + cooling system
EXAFLOPS? 100x 1.5 GW= 10% US power grid
DARPAmax: 20 MW 500 racks
4/2/2012
14
53
3 reactors melt-down
Simulations suggested that three nuclear piles
are in meltdown on March 13 but Japanese
government wont admit it for two months
Simulation by SPEEDI (System for Prediction
of Environmental Emergency Dose
Information) are accurate. The government
did not disclose the simulation data until
March 25.
Fukushima
54
Tsunami-coupled equation of motion in 3D
Maeda and Furumura (2011) Pure and Applied
Geophysicsunder review
Navier Stokes eq.
Present resolution: 1 km
CPU Time 2 hour
ES 64 node
Expected resolution: 0.25 km
CPU time < 5 min
(K Computer)
Ground motion and tsunami simulations
55
The radiation levels had spiked to harmful levels after a fire
and two more explosions at the site
56
Simulaciones no podan predecir el terremoto y tsunami
Sin embargo, simulaciones pueden ayudar a minimizar danos.
Simulaciones tendrn un gran impacto en el planeta y su gente en
por muchas generaciones en el futuro
Pero es importante que se confe sin trabas la informacin hacia el
publico
Este desastre a forzado a los cientficos a confrontar problemas de
alta dificultad: En el deseo de lograr mejores estilos de vida, no
siempre se tomaron las mejores decisiones.
En el Per, debemos decidir qu clase de sociedad queremos crear, y
as definir nuevos paradigmas
Confiabilidad sin barreras
4/2/2012
15
KComputerJapan
AsJune2011:
8.162petaflops (10
15
)
Fujitsu
June2011numberone
672racks
68,544CPUs
For2012:+80,000CPUs10petaflops
RAM:1petabyte
SPARC64VIIIfx (8cores,128gigaflops)
TOFU:6dimensionalmesh/torustopology
Each128Gflops
2.2Gflops/watt
Total~5Mwatts
825Mflops/watt
Total~1200Mwatts
The K supercomputer: Led by
RIKEN and built by FUJITSU is
wholly made in Japan
supercomputer. From R&D of
the processors to system design
and manufacturing.
4/2/2012
16
4/2/2012
17
Una molcula exhibe
un potencial
intrnseco V(r)
inducido por sus
electrones (r) y
ncleo (Z
i
)
}

= '
| ' |
) ' (
| |
) ( dr
r r
r
r R
Z
r V
i
i

EscenariodeMEPs
En la vecindad accesible del agua, el oxgeno muestra un potencial
negativo (rojo) y el hidrgeno positivo (azul). Se puede codificar y
procesar informacin al cambiar estos potenciales debido a las
interacciones con el potencial de otras molculas
4/2/2012
18
The GENIP procedure, in order to calculate the current I as a function
of the applied voltage V from first principles, includes the discrete
wavefunction of the extended molecule attached to the continuum
wavefunction of the electrodes; the two wavefunctions are mixed
through a Greens function procedure.
+V
I(V)
Molecular Ab-Initio
Gaussian
Extended Ab-Initio
Crystal
Electron Transport
GENIP
Molecular
Dynamics
LAMMPS
Circuit Simulator
SPICE
Process Simulator
ASPEN
Proof of
Concept
Experiments
Theory
Continuum Discrete
Interface
GENIP
Continuum-Discrete
Continuum analysis
Quantum&Classical
Meso-
Micro-
Nano-
molecular dynamics
Discrete Analysis
ab initio &
molecular dynamics
Macro-
electrons & nuclei electrons & nuclei electrons & nuclei
Vibronics
Current
Voltage
Molecular
Potentials
Agent
Sensing
Communications
Control
If the agents are molecules, the best detector is another molecule
4/2/2012
19
E
LUMO
=- 2.91 eV
E
HOMO
= - 4.65 eV
Molecular electrostatic
potential mapped on the
total density surface
0.5 eV -0.5 eV
Metal-Metal Interactions Sutton-Chen Potential (Phil. Mag. Lett.
1990)
Metal-Carbon Interactions SIMCAT reactive potential (J. Mol.
Modeling, 2007)
Carbon-Carbon Interactions Modified Tersoff-Brenner Potential
(reactive forcefield; J. Mol. Modeling,
2007)
Potenciales interatmicos
1
2
1
( ) ( )
2
tot ij ij
i j i
U V r c c c
=
(
=
(


( ) ( ) ( )
1.1
MC R MC A
ij ij ij ij
G V r V r o o =
74
) ( ) ( ) (
1 . 1
ij
A CC
ij ij
R CC
ij
r V r V G o o =
Molecular Dynamics simulation
Tersoff potential
Atoms interact for a period of time.
Allows material analysis at atomic scale.
Simulation requires the definition of a potential function.
For group III-V semiconductors the Tersoff potential is
suitable
We need to find the correct parameters for Si, Ga and As
system.
We need to define the simulation conditions.
pair distribution function
0
500
1000
1500
2000
0 0.5 1 1.5 2 2.5 3 3.5
g
r ()
PDF - LAMMPS
Corriente Voltaje
FuncindeTransmisin:
Probabilidaddequeun
electrnsetransfieraatravs
decanalesdeconductancia
h :ConstantedePlanck
e:cargaelctrica
E
f
: Energa de Fermi
( , , ) T E V | A A
( )
}
+
+
A A =
2
1
) , , (
2
V E
V E
f
f
dE V E T
h
e
V I |
Combinacin
Funcionalesde
DensidadyFunciones
deGreen
I
+ V -
4/2/2012
20
o-helix polyL-alanina
Localizacin de la carga causa
un dipolo intrnseco desde el C
a N-terminal
Corriente-voltaje de la polyalanina y el espectro de la energa de
los orbitales moleculares desocupados (azul) y ocupados
(negro)
o-helix polyglycina
Cristancho & Seminario JCP-2010
Se pueden usar para fabricacin de dispositivos
Polyglicina extendida
Corriente-Voltaje de la polyglicina
extendida
1 yA = 10
-24
A
atto, zepto, yocto
Los electrones se transportan a travs de los
puentes de hidrgeno
3D-electrnica
Armazn de DNA programable: DNA origami
Grupos fosfatos cargados pueden inmovilizar nano-
partculas
-31
-29
-27
-25
-23
-21
-19
-17
-20 -10 0 10 20
l
n
(
I
)
V
360K 320K
280K 240K
Corrientevoltajetemperatura
caracterstica del DNA origami
-42
-40
-38
-36
-34
-32
-30
2.7 3.2 3.7 4.2
l
n
(
I
/
T
2
)
103/T
20V
10V
5V
1V
-34
-32
-30
-28
-26
-24
-22
-20
2.7 2.9 3.1 3.3 3.5 3.7 3.9 4.1
l
n
(
I
/
V
)
103/T
20V
10V
5V
1V
Thermionic emision Hopping conduccion
Bobadilla et al. JCP 2009
4/2/2012
21
Una molcula exhibe
un potencial
intrnseco V(r)
inducido por sus
electrones (r) y
ncleo (Z
i
)
}

= '
| ' |
) ' (
| |
) ( dr
r r
r
r R
Z
r V
i
i

EscenariodeMEPs
En la vecindad accesible del agua, el oxgeno muestra un potencial
negativo (rojo) y el hidrgeno positivo (azul). Se puede codificar y
procesar informacin al cambiar estos potenciales debido a las
interacciones con el potencial de otras molculas
83
Nano and Molecular Electronics Group
Este trabajo muestra el uso del Potencial Electrosttico
Molecular (MEP) para formar lgica
-0.5V 0V 0.5V 1V
-1V -0.5V 0V 0.5V -1V -
0.5V
0V 0.5V
0
0
0
V < 0 0
V > 0 1
0
1
0
1
1
1
AND
gate
}

= ' dr
| ' r r |
) ' r (
| r R |
Z
) r ( V
i
i

MEP (V) es inducido por todos los electrones y ncleo Z
i
de un sistema
molecular
V provee una nica manera de codificar
informacin a escala molecular, el cual puede
ser modificado estratgicamente por la
presencia de otra molcula
Dgitos: 1 (positivo) & 0 (negativo)
Gates moleculares basados
en potenciales
electrostticos
0
0
0
0
1
0
1
1
1
0.5 V - 0.5 V
1 1
1
1 1
0 0
0
0
- 0.2 V 0.2 V - 0.1 V 0.1 V
AND: trifluorobenceno y agua OR: 1,1 diethynyletene y agua
Cascada
}

= '
| ' |
) ' (
| |
) ( dr
r r
r
r R
Z
r V
i
i

0
1
2
3
4
5
0 0.5 1 1.5 2
Voltage (V)
C
u
r
r
e
n
t
(
u
A
)
=0 =15
=30
=45
=60
=90
=75
0 90 0 90
La corriente a travs del OPE decrece
conforme el anillo central rota
Graphite Silicon
AND gate OR gate Isolated: OR gate
Efecto del substrato
4/2/2012
22
Nanomicrointerface para leer el
potencial molecular en
electrnica basada en corriente-
voltaje
2A, 49.7
3A, 136.7
2A, 0
3A, 0
-5
-3
-1
1
3
5
-2 -1 0 1 2
Voltage (V)
C
u
r
r
e
n
t (u
A
)
2A, 54.7
3A, 139.6
2A, 0
3A, 0
-5
-3
-1
1
3
5
-2 -1 0 1 2
Voltage (V)
C
u
r
r
e
n
t
(
u
A
)
2A, 55.8
3A, 143.3
2A, 0
3A, 0
-5
-4
-3
-2
-1
0
1
2
3
4
5
-2 -1 0 1 2
Voltage (V)
C
u
r
r
e
n
t (u
A
)
Positivo-Positivo
Positivo-Negativo
Negativo-Negativo
Corriente a travs del OPE depende: rotacin
del anillo central & distancia del gate OR
Grafeno:SuperficiePlasmnica
LUMO 2.91eV HOMO 4.65eV
Densidad
electrnica
total