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Useful Nanotechnologies Based on Molecular Information Handling
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Useful Nanotechnologies Based on Molecular Information Handling
Robot: A machine or device that operates automatically or by remote control
Computer: A device that ... processes information
Ion-Switchable Fluorescence
SpacerM+
Fluorophore Receptor
Constant Fluorescence
Fluorophore
SpacerFluorophore Receptor
< 1 nm
> 1 nm
Luminescent molecular switchable systems can gather and process information
Optical response
Chemical stimulus level
Analog region
Digital 1
Digital 0
The Miniature James Bond
Luminescent Sensing
OFF state
Spacer
hν
PET
Fluorophore Receptor
ON state
hν
PET
hν
M+SpacerFluorophore Receptor
The PET design generalized in Colombo/BelfastChem. Rev. 1997, 97, 1515
Org. Biomol. Chem. 2008, 6, 2468
Imperiali,Marcus,Cary
Stoddart,
Selinger
Shinkai, Kubo,Hamachi
Fabbrizzi, Quici,
Rettig, Resch, Wolfbeis, Daub,
Verhoeven
Bouas-Laurent, Desvergne,Lapouyade, Fages, McClenaghan
Balzani, Prodi,Barigelletti, Campagna,
Soumillion
Bharadwaj, Khan
Zinic
Samanta
Grigg, Moore, Brown, James, Davidson, Beer,Stoddart, Parker, Williams, Ward, Sutherland
Kuhn,
Yang
Czarnik, Pearson
Morawetz, Pardo
Masilamani
Turro,
Garcia-Espana,Costero,Miranda,Escriche,Luis, Perez-Inestrosa
D’SouzaInoue
Brown
Gawley, Leblanc
Lakowicz, Pu
Roche, Fahrni
Wang, Lindsey
Roche
Wang, Ma,
Moller, Rurack, Schuster, Greiner
Reymond
Ji
Kumar
Rajasekharan,Ajayaghosh,Ramaiah, Varma
Lawrence, Adams,
Qian
Das
Lincoln
Walt, Miller,Lippard
Smith Jin Qian, Tian,Chen
Bianchi,Pallavicini
Lippolis
Akkaya,Valkan
Koide
Chattopadyay
Hsu, Chiu
Whitten
Leigh,Callan
Plater,
Gunnlaugsson,O’Shea, Kruger
Bruckner
Shizuka, Teramae,
Chatterjee, Kimura, Osa, Sakamoto, Iwai,Nakatsuji, Fukuzumi,
Tanaka, Nagano,Imai, Nagamura,AkasakaGee
Chang
Tsien,Barbas,Rebek
Kulatilleke
de Silva,McCoy
Pina, Pischel,Lodeiro
Shanzer,Eichen,Willner
Wu, Li, Chen,
Chang,
KimYoon,
Bhattacharya,Maitra
Guo, Lin
Tang
de Silva
Diaz-Fernandez
Valeur, Lehn,Weiss, Leray
Jiang
de Silva,
Kruger
Pfeffer
Yagi
Levine,
Anslyn, Demas
Kotschy, Kele
Bojinov,Grabchev
Lu
Sung
Suzuki,Holdt, Plenio, Sauer
Nielsen, Kilsa
Yunus,Hofkens
Hall, Watkinson
Meallet,Mallet,Vicens
Ghosh Zhu, Wang,
Kim, Hong,
Zuo, Guo,Huang, Liu,
Yao, Fu
De Costa
Wainwright
Yoshida,Ooyama,Sasamoto
Todd
Nakamura
Saleh
Seeberger
Mashraqui
Hancock
Ramamurthy
He, JiYou
Houston
Heagy
Cho
Burdette
Lin
Magri
Rudkevich
Sango Toyooka
‘Off-On’ sensors selective for
Na+ and K+
Jim Tusa, Marc LeinerHua-Rui He, Mark Mortellaro (Roche)
J. Mater. Chem. 2005, 15, 2640
hydrophilic polymer O
O
O
N
HN
O
O
N
O
N
O
N
O O
O O
hydrophilic polymer
N O
OO
O
O
NH
N
O
O
O
Sodium Potassium
receptor
hydrophilic polymerhydrophilic polymer
spacer
fluorophore
linker
Disposable Cassette and OPTI Critical Care Analyzer (CCA)
Na+ K+ Ca++ or Cl-
CO2 O2 pHtHb
60M USD Cassette sales
ambulances, hospitals, GP and vet surgeries
NEt2
NEt2
O NN
NHNEt2
Fluorescent PET pH Sensors
LysoSensorTM Blue and Green (Molecular Probes)
DAYA RUPASINGHE
NIMAL GUNARATNEJ. Chem. Soc., Chem. Commun. 1985, 1669
Cancer cells respond to radiation by developing acidic vesicular organelles. Sensor: Lysosensor Blue Paglin et al (Sloan-Kettering Center, NY) Cancer Res. 2001, 61, 439
18µm
Robots for Mapping
Small Nanospaces
Seiichi Uchiyama (University of Tokyo)Kaoru Iwai (Nara Women’s University)Angew. Chem. Int. Ed. 2008, 47, 4667
A Popular Robot
A Useful Robot Mars Rover‘Opportunity’January 2005
‘Phoenix’ May 2008
fluorophore spacerreceptorICT
fluorophore spacerreceptor
HH+
fine positionergross positioner
NS
O ON
ON
NH
N
OOH
10
.S1
thexiS1
thexi
S0
FC
S0
FC
non polar solvent polar solvent
+ +
E
.Solvent Polarity Effect on ICT Fluorescence
hexaneCH2Cl2
CH3OHIf
λ
450 500 550 600 650 700 750 800
0
pH
Wavelength (nm)
IF
20 30 40 7050 600
–0.4
–0.8
–1.6
–1.2
20 30 40 800
–0.4
–0.8
–1.2
p
p
100
–0.4
–
–
–
10 20 40 50 60 70
–
–
–1.2
pΔpKa
Δ Ka
80
OOH
10
O
OH
OH
OHO
OH
Polarity ( ε)
Polarity ( ε)
generalization
integration
numeracy
games
reconfiguring
object identification
improved sensing
MolecularLogic Gates
Nature 1993, 364, 42Nature Nanotechnol. 2007, 2, 399
George Boole1849-64, Cork
Kim, Yoon, Jang,Choi, Zhang
Rurack,
Desouter-Lecomte, Lehn
Bouas-Laurent, Desvergne,Bassani, McClenaghan
Balzani, Credi, Venturi, Gentili
Bharadwaj, Khan
Samanta
Adleman,Ghadiri,
de Silva,
Pina, Pischel
Garcia-Espana,
BrownRaymo, Zhu
Akkaya
Ji
Gunnlaugsson,MacDonaill
Birge, Stojanovic,Seeman,Avouris,Katz, Sokolov, Privman
LangfordStefanovic,
Wasielewski,
Levine, Speiser,Shanzer,Willner,Shabat,Ashkenasy,Lotan,Van der Boom,Rabani, Shapiro, Eichen
Konermann
Remacle
Reif
Diederich,Constable, Schluter
de SilvaWettig
Perez-Jin
Schneider,
Uchiyama, Aida,
Leigh,Callan
James, Stoddart, Parker, Beer, Chin, Jones,Williams, Tucker, Zauner, Fallis, Aldridge, Steed
Szacilowski
Chiu
Gust, Moore
Steer, Iwai, Okamoto,Sugimoto, Hirai,
Redmond,
Miranda
Kimura
Miyashita, Suzuki
Tian, Wang, Jin,
Lu
Lerner,Barbas,Wang
Wu
Toma
Conrad, Liu
Bazan
Andreasson, Sun
Liu
Tanaka, Fujita,
Breaker,
Das
Kumar
Lu
Zhang, Zhu, Yan, Li, Fu,
Huang, Zhang,
Mihara, Nojima,
Tomizaki, Matsui,
Pischel
Fujimoto, Akashi
Qian, He, YuYang
Benenson
Stoddart,
Vasquez-Lopez
Yuan, Fang,Voegtle
Shi, Tong,Wang
Kinbara, Ariga,
Magri
Yurke
Yeow, Hamilton
Doorn
Hill, Miyashita,
Stoddart,Smith,
Zink,
Heath, Smolke
Walt,
Pandey
MatsuiInestrosa,
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 φF
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
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 µm 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
J. Am. Chem. Soc. 2007, 129, 3050
Parallel Processing of Analog Sensory Information
Sisira de Silva, Nalin Goonesekera, Suram Patuwathavithana,
Sydney Ramyalal (Colombo) Nimal Gunaratne, Mark Lynch, Kemuel Nesbitt
RECEPTOR 1
SPACER
FLUOROPHORE
RECEPTOR4
SPACER
FLUOROPHORERECEPTOR 3
SPACER
FLUOROPHORE
RECEPTOR2
SPACERFLUOROPHORE
ΣIF
pH
Parallel processing to produce greatly increased dynamic range
NR1R2
NR1R
2
a ; R1= R2 = CH2CH3
b ; R1= R2 = CH2CH2OHc ; R1 = H, R2 = CH2CH2N(CH2CH3)2d ; R1, R2 = CH2CH2N(CH3)CH2CH2
1.4404, 426, 443 (0.56, 0.008)393(4.01), 372(4.01), 353(3.76)d
4.1404, 426, 443 (0.55, 0.014)395(4.03), 374(4.03), 355(3.81)c
6.1405, 427, 445 (0.56, 0.005)395(4.10), 374(4.09), 355(3.87)b
8.1405, 427, 445 (0.59, 0.004)393(4.03), 372(4.02), 353(3.81)a
pKa Emissionλ (φmax , φmin)
Absorption λ (log ε)
0 42 86 10
0
20
60
40
100
80
Σ IF
pH
390 5000
Wavelength (nm)
Σ IF
100
“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
_
_
_
_
_
_
_
_
_
_
_
_
_
__
__ _
_
_
_
_
_
_
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_
_
_
_
_
_
_
_
_
_
_
__
_ _
__
__
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 βCa2+ = 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 βCa2+ = 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
- -
ProvidenceProvidence
LuckLuck
SerendipitySerendipity
EPSRCEPSRC
DENIDENI
EUROPEAN COMMISSIONEUROPEAN COMMISSION
JAPAN SOCIETY FOR JAPAN SOCIETY FOR THE PROMOTION OF SCIENCETHE PROMOTION OF SCIENCE
