novel nano-architectural concepts for thz/ir … nano-architectural concepts for thz/ir based...

Novel Nano-Architectural Concepts for THz/IR Based Bio-Sensing

Dwight L. Woolard

U.S. Army Research Office

Presentation to:

CREOL, The College of Optics & Photonics, Industrial Affiliates Day – 2011

Far IR & Terahertz Photonics

April 29, 2011 Orlando, Florida

James O. Jensen

U.S. Army ECBC Greg Recine

Fordham University Alexei Bykhovski & Weidong Zhang

N.C. State University

Presentation Outline

Science & Technology Objective: “THz-Sensitive” Material Systems

Motivation & Context: THz Sensing Science & Technology

Research on Organic Systems: Molecular (Benzene) Ring Derivatives

Research on Biological Systems: DNA (Stilbene) Derivatives

HBOF Smart Material Paradigm: Antibody & Receptor Mimics (HBOF = Hybrid Biological-Organic Functionalized)

Conclusions: Future Directions in the Research







Science & Technology Objective

Identify and quantify novel molecular-level functionality

useful for engineering “THz-sensitive” material systems.

THz-sensitive – THz regime electronic and/or photonic material properties are

dictated in a predictable manner by the functionality paradigms.

In the context of Biological Targets:

Organic Switches: Engineered Reaction to Bio-Targets (i.e., dipole)

Biological Switches: Engineered Reaction by Inclusion of Bio-Targets

Overall objective is to extract nanoscale information (e.g., composition, dynamics,

conformation) through electronic/photonic transformations to the macroscale

Organic Switch Concept – Indirect Transduction via Readout of Target

Biological Switch Concept – Direct Transduction via Dependency on Target

Bio-Molecular Architectures:

Synthetic Antibody (Capture) & Receptors (Capture/Report)

Science & Technology Objective

Fig. 1.

Fig. 2.



Fig. 3.
















ti

Recent Real-World Origami Construct (Norton, Marshall University)

Hypothetical DNA-Based Unit Cell

with OMS-Induced Anisotropic Dielectric

OMS Functionalized Material Concept

Organic Molecular Switches (OMS)

for Engineering Functional Electronic Materials

Illustration of Target-Molecule Induced

Dielectric-Tensor Refraction Effect Response




Recent Real-World Origami Repetitive-Constructs (Norton, Marshall University)

nt Real World Origami Repetitive Constr




Linear chains of carbon (n-alkanes) terminated by sulfur (thiol)

101 Carbons: n-Thiohenihectane (C101H204S2)

Basic Concept for Long-Chain OMSs

Long-Chain OMSs Afford:

Theoretical Advantages (e.g., Plane Wave Solutions)

Analogies to Traditional Solid-State Electron Devices




Replace H by two OH groups l H b t OH



Functionalized Long-Chain OMSs

2

3

4

5

6

7

8

9

10

0 5 10 15 20

Ene

rgy

(eV

)

Level Above LUMO

GAMESS Simulations, Hartree-Fock, 6-31G** split-valence type basis

0 to 90 degree rotation - Small to Large Squares

1

)

Three Benzene Rings (OOO)

Initial Test Case Only – No Dipole 2

3

4

5

6

7

Ene

r

rgy

(eV

Initial Test Case Only – No Dipole





GAMESS Simulations, Hartree-Fock, 6-31G** split-valence type basis

4.4

4.6

4.8

5

5.2

5.4

5.6

5.8

6

6.2

0 20 40 60 80 100 120 140

Ene

rgy

(eV

)

Position (Å)

Natural State

0 to 90 degree rotation Small to Large Squares

Functionalized Long-Chain OMSs

5

5

6

V)

Three Benzene Rings (OOO)

Initial Test Case Only – No Dipole 4.4

4.6

4.8

5

5.2

5.4

5.6

Ennnnnnnnnnne

5

5

5

rgy

(eV

Initial Test Case Only – No Dipole

Functionalized Long-Chain OMSs: DC Conductivity Characteristics

Zero-, Low- & High-Frequency

Conductivity estimated from

Marcus Theory, electron hopping transport

Marcus Theory ~ Flexible System

As compared to

Mott Theory ~ Stiff System

Goal: determine the potential for

invoking large changes in the

dielectric properties of material



Marcus Theory: Electron Hopping Between Two Defect States

Before Transition After Transition

Marcus Transition Mott Transition



Functionalized Long-Chain OMSs: Frequency Dependent Conductivity Characteristics

1.0E-54

1.0E-48

1.0E-42

1.0E-36

1.0E-30

1.0E-24

1.0E-18

1.0E-12

1.0E-06

1.0E+00

1 100 10000 1000000 100000000 1E+10 1E+12 1E+14

Co

nd

ucti

vit

y(S

/cm

)

Freq. (Hz)

0

10

20

30

40

50

60

70

80

90

DC + A 1 s + PA ( )




1.0E-54

1.0E-48

1.0E-42

1.0E-36

1.0E-30

1.0E-24

1.0E-18

1.0E-12

1.0E-06

1.0E+00

1 1000 1000000 1E+09 1E+12

Co

nd

ucti

vit

y(S

/cm

)

Freq. (Hz)

~50

~150

From THz Sensing Technology, Volume II

World Scientific, 2003

( ) =n0377

1015




x

y

z

Relying only on Low-Frequency results

GHz( ) 10 6 S cm

r( ) =1+ i10 6

0

Drude Model

0

r @1THz( ) =1+ i10 6

To Realize a Major Dielectric Change

r @1THz( ) =1+ i 1or 0( )

10 switches per Aperture (@ 100 nm unit cell size) (@ 100 n

Or, Unit cell size = 10 nm

Per unit area filling only ~ 10-14/ cm2



What about Compound Ring Structures?




What about Compound Ring Structures?


1.00E-20

1.00E-18

1.00E-16

1.00E-14

1.00E-12

1.00E-10

1.00E-08

1.00E-06

1.00E-04

1.00E-02

1.00E+00

1.0E+00 1.0E+03 1.0E+06 1.0E+09 1.0E+12

Co

nd

ucti

vit

y(S

/cm

)

Freq.(Hz)

0

10

20

30

40

50

60

70

80

90



Functionalized Long-Chain OMSs: Major Optimization Issues

Advantages of Compound Ring Structures?

Energy Levels (energy/spatial position & dependency on ring rotation); Polarity & Interaction of Rings

Best Aromatic (C Ring) Derivatives?

Energy Levels (position relative to barrier & dependency on ring rotation); Polarity of Ring



1

2

3

4

5

6

7

8

0 5 10 15 20

Ene

rgy

(eV

)

Level Above LUMO



Functionalized Long-Chain OMSs: Aromatic Derivatives (Good Energy Ladder, Strong Dipole)

Benzoyl Chloride



Functionalized Long-Chain OMSs: Benzoyl Chloride

0.0E+00

5.0E-10

1.0E-09

1.5E-09

2.0E-09

2.5E-09

3.0E-09

3.5E-09

0 20 40 60 80 100

co

nd

ucta

nce(o

hm

^-1

)

angle

Single-Defect Conductivity Estimates: DC, Low-Frequency & High-Frequency

1.00E-42

1.00E-36

1.00E-30

1.00E-24

1.00E-18

1.00E-12

1.00E-06

1.00E+00

1 100 10000 1000000 100000000 1E+10 1E+12 1E+14

co

nd

uc

tiv

ity

(S

/cm

)

Freq. (Hz)

0

10

20

30

40

50

60

70

80

90



Functionalized Long-Chain OMSs: Benzoyl Chloride

Multiple-Defect Conductivity Estimates: DC, Low-Frequency & High-Frequency

1.0E-16

1.0E-14

1.0E-12

1.0E-10

1.0E-08

1.0E-06

1.0E-04

1.0E-02

1.0E+00

1.0E+00 1.0E+03 1.0E+06 1.0E+09 1.0E+12

co

nd

uc

tiv

ity

(S/c

m)

Freq. (Hz)

0

10

20

30

40

50

60

70

80

90

Motivation & Context

~ 2005 ~ 1995


Biological Molecular Switches (BMS)


DNA-Derivative Paradigm of Interest: Stilbene-functionalized Single- and Double-Stranded DNA

TMS - trimethoxystilbene carboxamide

TMS has been used previously to define optical nanoscale sensors where

the fluorescence was dependent upon exposure to proteins & DNA.

TMS conformation dependent on binding?



Hybrid QM(HF & DFT)/MM Simulation of Switchable Functionality in Stilbene-DNA Conjugates



Light-Induced Pathways for Switching: Advanced Optimization + Human Interface

New (n-D) Simulation Tool Development

D5 D8

Simple (1-D) Light-Induced Transformation

Similar to process in vision



A New Light-Induced Pathways in Stilbene?: 0-1-2 Energy States & 5 Coordinates Optimization

New (n-D) Simulation Tool Development Simple (1-D) Light-Induced Transformation

Similar to process in vision



A New Light-Induced Pathways in Stilbene?: 0-1-2 Energy States & 5 Coordinates Optimization

Basic Structural Paradigm: DNA Nanoscaffold + Functional DNA-Derivative Elements

DNA Parallelogram Motif for 2-D

N.C. Seeman. Nanotechnology and the Double

Helix, Scientific American., 290, (6) 64-75 (2004).

Seeman Group (NYU) & Norton Group (Marshall) working Towards 3-D









Conclusions: Future Directions in the Research Conclusions: Future Directions in the Research






HBOF Smart Material Paradigm: Antibody & Receptor Mimics

Previous OMS & BMS define new paradigm for Synthetic Antibody & Receptors

Compound Rings

can Report DNA Derivatives can

Capture on Command

DNA Deriva

C t C

Hybrid OMS/BMS

Can be Defined

Both Useful for

(1) Reagent-Based Recognition

(2) Reagentless, Spectroscopic

Monitoring & Sensing


A Proposed Antibody (DNA Aptamer Capture) Mimic with OMS Reporting

Thrombin-aptamer system (TAS)

Thrombin DNA aptamer G15D, with

sequence GGTTGGTGTGGTTGG


A Proposed Receptor (Ring Capture & Ring Reporting) Mimic

Phenylpyridyl capture system,

where Y influences the binding target.


A Proposed Receptor (Ring Capture & Ring Reporting) Mimic

organophosphorus compound Sarin (i.e., X=F,

R=Isopropyl) are shown along center.

Two perpendicular views of the stable molecular conformations are given

above and below, respectfully.

State (A) is the natural conformation of the

the isopropyl methylphosphonate anion (denoted as

A ) where a temporary electro-static binding occurs between the two.

The scheme is relevant to organophosphate gases (nerve agents) Sarin, Soman & Tabun and

the model compounds of lesser toxicity disopropylfluorophosphate (DFP) and

diethylchlorophosphate (DCP)) but that possesses a natural capture/report functionality that can be fluorescence tested by reaction with the less toxic compound thionyl chloride (SOCl2).

It should also produce an energy ladder structure (i.e., create a defect) near the center of the

double-ring, and be useful as an OMS reporter.

Conclusions – Future Directions

Molecular Synthesis

Electro-Optics

Molecular

Architectures Bio-Threat Detection

Recognition

Chemistry

Smart

Materials Bio-Threat Recognition

& Characterization

Bio-Science &

Immunology

Bio-Threat

Counters & Treatment

Artificial

Vaccines

novel nano-architectural concepts for thz/ir … nano-architectural concepts for thz/ir based...

Documents