Design and Applications of Luminescent Logic Systems

generalization

integration

numeracy

games

reconfiguring

object identification

improved sensing

MolecularLogic Gates

Nimal Gunaratne, Colin McCoyNature 1993, 364, 42

George Boole1849-64, Cork

Kim, Yoon,Choi, Zhang

Lehn

Bouas-Laurent, Desvergne,Bassani, McClenaghan Balzani, Credi,

Venturi, Gentili,

Bharadwaj, Khan,

Samanta

Adleman,Ghadiri,

de Silva,Yurke

Pina, Pischel

Garcia-

Brown

Raymo, Zhu,

Akkaya

Ji

Gunnlaugsson,MacDonaill

Birge, Stojanovic,Seeman,Avouris,Katz, Privman,Sokolov, Wang

Langford,Stefanovic,

Wasielewski,

Levine, Speiser,Shanzer,Willner,Shabat,Ashkenasy,Lotan,Van der Boom,Rabani, Shapiro, Eichen

Konermann Remacle

Reif

Diederich, Constable, Schluter

de SilvaWettig

Inestrosa,Jin

Schneider, Rurack,

Uchiyama, Aida,

Leigh,Callan

James, Stoddart, Parker, Beer, Chin, Grigg,Williams, Tucker, Zauner, Fallis, Aldridge

Szacilowski,

Chiu

Gust, Moore

Steer, Yeow,

Iwai, Okamoto,Sugimoto, Hirai,

Redmond,

Miranda,

Kimura,

Miyashita

Tian, Wang, Jin,

Lu, Ma

Lerner,Barbas,

Wu

Toma

Conrad, Liu, SmithBazan

Andreasson, Sun

Liu

Tanaka, Fujita,

Breaker,

Das

Kumar,

Lu

Zhang, Zhu, Yan, Li, Fu,

Huang, Zhang, Yu,

Mihara, Nojima,

Tomizaki, Matsui,

Pischel

Fujimoto, Akashi,

Qian, He

Yang

Benenson, Walt

Stoddart, Heath, Smolke

Vasquez-Lopez

Yuan, Fang,Voegtle, Schmittel,

Shi, Tong,

Hamilton

Doorn

Wang, Xing,

Kinbara

Miyashita, Hamachi

Samoc

Callan,

Perez-

Espana,

CoveraKolpashnikov,

Ihmels, Theato

Wang

Bhalla,

Upadhyay

Wu, Shi

Singh

Pallavicini, Fabbrizzi,

Kubo

Campagna, Quici

Evans

Johnson

D’Souza

JiaSuzuki, Araki

Budyka

Alexander, Jones, Steed

Nandi

Jang

Alfonta

Humphrey

Magri

Hill, Ariga

Stoddart

Zink,

deSouter-Lecomte

Pasparakis

PandeySiri

Mayer, Nau, Schalley,

Dwyer

Sessler, Tour

Jiang

Ha, Lee, Kim, Oh

Plaxco

Seeberger, Schiller

Kandaswamy

Jiang

Zhang

Wang, Qu,Dong, Ren,

Zhu

Yamada, Ogawa,

Kong,

Ruiz-Molina

Huang

Zhang, Ye,

Pita

Ajayaghosh

Maeda

Tuntulani

Shvarev

HanleyDarwish,

Stokke

Wang, Jiang, Hu

Cheng

Leung

Flood

011

100

OUTOUTIN

NOTYES

IN IN

OUT OUT

111

001

010

000

OUTIN2IN1

AND

IN1 IN2

OUT

Luminescent molecular switchable systems can gather and process information

Optical response

Chemical stimulus level

Analog region

Digital 1

Digital 0

Molecular Computation in a Small Nanospace

Seiichi Uchiyama, Gareth McClean,Kaoru Iwai (Nara Women’s University)

J. Am. Chem. Soc. 2005, 127, 8920

3 nm

Soap micellewith ion cloud

O

OO

O

O

N

fluorophorespacer spacerreceptor2

anchor

Na

receptor1

H

fluorophorespacer spacerreceptor2

anchor

Na+

receptor 1

H+

OSO3 N

400 5000

400 500Wavelength (nm)

HH+

Na+

HH+

Na+

none

and

IF

Combining Several Diagnostic Tests and Data Processing

in a “Lab-on-a-Molecule”

David Magri, Gareth McClean, Gareth Brown

J. Am. Chem. Soc. 2006, 128, 4950

Full Blood CountDate : 20.08.2005

Description Result Units Reference Ranges RemarksHaemoglobin 8.70* g/dl 12.00 17.50 LowRBC 2.34* x 10x6/mm3 3.50 6.00 LowPCV 26.70* % 40.00 54.00 LowMCV 114.10* fl 70.00 96.00 HighMCH 37.20 pg 27.00 32.00 HighMCHC 32.60 g/dl 30.00 ….35.00 …NormalPLATELETS 140,000.00 mm3 150,000.00 450,000.00 LowWBC 8,200.00 mm3 4,000.00 11,000.00 NormalNEUTROPHILS48.00 % 40.00 75.00 …normalLYMPHOCYTES48.00 % 10.00 45.00 HighEOSINOPHILS 2.0 % 1.00 6.00 NormalMONOCYTES 2.00 % < 10.00 Normal

Performed by Sysmex/Hycell Automated Haematology Analyzers

Logical combination of ‘high’ and ‘low’

parameters identifies disease

Spacer ReceptorReceptor Spacer SpacerFluorophore Receptor

O

OO

O

O

N

N CO2

CO2

-

-

HH+Na+

Zn2+

Wavelength / nm

400 440 480 520

+

Na+ , H+ , Zn 2+

Na+ , H +

Na+ , Zn 2+

Na +

H+ , Zn 2+

Zn 2+

H

No inputs

0

IF

1 (high, 0.020)1 (high)1 (high)1 (high)

0 (low, 0.006)1 (high)0 (low)1 (high)

0 (low, 0.007)0 (low)1 (high)1 (high)

0 (low, 0.006)0 (low)0 (low)1 (high)

0 (low, 0.003)1 (high)1 (high)0 (low)

0 (low, 0.002)1 (high)0 (low)0 (low)

0 (low, 0.001)0 (low)1 (high)0 (low)

0 (low, 0.001)0 (low)0 (low)0 (low)

Output Fluorn F

Input3

Zn2+

Input2

H+

Input1

Na+

3-Input AND Logic Truth Table

Molecular Computational Identification (MCID)

of Small Objects in Populations

Sheenagh Weir, Bernie McKinney Dave Pears, Mark James (Avecia)

Nature Mater. 2006, 5, 787

Radiofrequency Identification (RFID): The semiconductor technology approach to identifying

each object (Goods, People) in an entire population

1 mm x 1 mm RFID chip (Hitachi)

EXCITATION WAVELENGTH: 368 nm

NNH

O

500Wavelength (nm)

Flu

ore

scen

ce

Inte

nsi

ty

385

100 Increasing pH

422

401

446

Prefabricated YES logic gate fixed to polymer bead (0.1 mm)

0

Prefabricated logic gates fixed to polymer beads

NNH

O

YES O

NH

PASS 1NO

NH

NOT

0

3 5 7 9 11pH

100

IF

1

YES

PASS 1

NOT

Arraying gates with identical fluorophores

and different logic type

2.5 % loading 2.5 % loading

Wavelength (nm)385 500

100

Increasing pH

422

401 446

O

NH

NNH

O

0

IF

PASS 1 YES PASS 1 + YES

Input(H+)

Output (Fluorescence)

Output (Fluorescence)

Total Output(Fluorescence)

0 1 0 1

1 1 1 2

pKa : 4.4

0

20

40

60

80

100

2.5 4.5 6.5 8.5 10.5

pH

Em

iss

ion

(at

422

nm

)

OUT( Blue fluorescence)IN

(H+)OUT( Blue fluorescence)

Multi-valued logic is available for molecular computational identification c.f. binary logic needed in semiconductor computing

Combinations of:Many (>5) excitation colours

Many (>5) emission colours

Many (>5) types (YES, NOT, PASS 1, AND,…)

Many (>5) chemical inputs (H+, Na+,…)

Many (>2) thresholds (pH 7, pH 4,…)

Many (>5) combinations (YES + PASS 1, YES + 2 PASS 1,…)

Conservatively, millions of m objects can be encoded!

acid

alkali

A

A

B

B

C

C

D

D

E

E

F

F

G

G

I

I

J

J

A; PASS 1 B; NOT C; PASS 1 D; PASS 1 + YES (1:1) E; YES F; NOT G; PASS 1I; YES J; PASS 0

“Plug-and-Play” Logic via Self-Assembly

Vinny Vance, Catherine Dobbin, Boontana Wannalerse

Chem. Commun. 2009, 1386

_

_

_

_

_

_

_

_

_

_

_

_

_

_

_

_

__ _

__

__

R

L

S RL

Self-Assembled YES Logic:

Covalently bound YES Logic:

Assembler: Non-ionic Detergent Micelle

N

N

2

N

N

n-C9H19

n-C9H19

RuII

OOH

10

O-

Long-lived (100 ns) lumophore

O-

pKa = 9.9

_

_

_

_

_

_

_

_

_

_

_

_

_

_

_

_

__ _

__

__

R 1

L

R2

SS R1L R2

Self-Assembled AND Logic:

Covalently bound AND Logic:

O-

N

CO2 CO2

On-C8H17

- -

pKa = 9.9 pKa = 5.8 Log Ca2+ = 1.5

11; 10-8 M H+ and 0.2 M Ca2+ 01; 10-12 M H+ and 0.2 M Ca2+

10; 10-8 M H+ only

00; 10-12 M H+ only

O-

N

CO2 CO2

On-C8H17

- -

_

_

_

_

_

_

_

_

_

_

_

_

_

_

_

_

__ _

__

__

R

L

S RL

Self-Assembled OR Logic:

Covalently bound OR Logic:

Non-selective Receptor

N

CO2 CO2

On-C8H17

- -

binds H+ or Ca2+

pKa = 5.8 Log Ca = 1.5

11; 10-4 M H+ and 0.2 M Ca2+ 10; 10-4 M H+ only

01; 10-8 M H+ and 0.2 M Ca2+

00; 10-8 M H+ only

N

CO2 CO2

On-C8H17

- -

Logic Gates withTemperature Input

Seiichi Uchiyama, Narumi KawaiKaoru Iwai (Nara Women’s University)

J. Am. Chem. Soc. 2004, 126, 3032

Temperature-sensitive co-polymer

O

O

N

SO2NMe2

NO

N

Co-polymerizable polarity sensor(Emission weakens in water)

NH

O

NMe2

NH

O

and

20 30 40

Temperature / C

0

IF

10

pH 7

●

20 40 60

Temperature / C

0 80

pH 9

pH 8

pH 7

pH 5

0

IF

2-Input INHIBIT Logic Truth Table

0 (low; 1)1 (high; 10-5 M)1 (high; 35 C)

1 (high; 10)0 (low; 10-9 M)1 (high; 35 C)

0 (low; 1)1 (high; 10-5 M)0 (low; 10 C)

0 (low; 1)0 (low; 10-9 M)0 (low; 10 C)

Output

Fluorescence

Input2

H+

Input1

Temperature

ProvidenceProvidence

LuckLuck

SerendipitySerendipity

EPSRCEPSRC

DENIDENI

EUROPEAN COMMISSIONEUROPEAN COMMISSION

JAPAN SOCIETY FOR JAPAN SOCIETY FOR THE PROMOTION OF SCIENCETHE PROMOTION OF SCIENCE