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Design and Applications of Luminescent Logic Systems. Molecular Logic Gates Nimal Gunaratne, Colin McCoy Nature 1993, 364 , 42. generalization. integration. numeracy. games. reconfiguring. George Boole 1849-64, Cork. improved sensing. object identification.
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Design and Applications of Luminescent Logic Systems
Molecular Logic Gates Nimal Gunaratne, Colin McCoy Nature 1993, 364, 42 generalization integration numeracy games reconfiguring George Boole 1849-64, Cork improved sensing object identification
Miyashita Kim, Yoon, James, Stoddart, Parker, Beer, Chin, Grigg, Williams, Tucker, Zauner, Fallis, Aldridge Andreasson, Sun Choi, Zhang Iwai, Okamoto, Schneider, Rurack, Wu Sugimoto, Hirai, Voegtle, Schmittel, Steer, Yeow, Tomizaki, Matsui, Benenson, Walt Ihmels, Theato Yuan, Fang, Leigh, Wettig Callan, Fujimoto, Akashi, Zhang, Zhu, Callan de Silva Miyashita, Hamachi Yan, Li, Fu, de Silva, Yurke Redmond, Shi, Tong, Uchiyama, Aida, Szacilowski, Gunnlaugsson, MacDonaill Wang, Xing, Tanaka, Fujita, Samoc Konermann Vasquez- Wu, Shi Mihara, Nojima, Remacle Wasielewski, Lopez Kinbara Lehn Lu Conrad, Liu, Smith Pina, Pischel Birge, Stojanovic, Seeman, Avouris, Katz, Privman, Sokolov, Wang Kimura, Levine, Speiser, Shanzer, Willner, Shabat, Ashkenasy, Lotan, Van der Boom, Rabani, Shapiro, Eichen Jin Bazan Perez- Stoddart, Heath, Smolke Kubo Inestrosa, Tian, Wang, Jin, Liu Pischel Huang, Zhang, Yu, Adleman, Ghadiri, Qian, He Reif Garcia- Espana, Chiu Lerner, Miranda, Barbas, Raymo, Zhu, Bharadwaj, Khan, Covera Kolpashnikov, Wang Upadhyay Johnson Lu, Ma Samanta Breaker, Yang Hamilton Brown Ji Toma Gust, Moore Akkaya Bouas-Laurent, Desvergne, Bassani, McClenaghan Das Balzani, Credi, Venturi, Gentili, Langford, Stefanovic, Doorn Evans Kumar, Diederich, Constable, Schluter Pallavicini, Fabbrizzi, Bhalla, Campagna, Quici Singh
Dong, Ren, Alexander, Jones, Steed Stokke Kong, Wang, Qu, Zhu Jiang Mayer, Nau, Schalley, Seeberger, Schiller Jang Budyka Stoddart Ha, Lee, Kim, Oh Flood Wang, Jiang, Hu deSouter-Lecomte Magri Suzuki, Araki Shvarev Jia Pita Hill, Ariga Alfonta Zhang Zink, Dwyer Yamada, Ogawa, Plaxco Siri Pandey Maeda Ruiz-Molina Nandi Cheng Pasparakis D’Souza Jiang Sessler, Tour Zhang, Ye, Leung Darwish, Hanley Huang Tuntulani Humphrey Ajayaghosh Kandaswamy
IN IN IN1 IN2 OUT OUT OUT YES NOT AND IN1 IN2 OUT IN OUT OUT 0 0 1 0 0 0 1 0 1 0 1 0 1 0 0 1 1 1
Luminescent molecular switchable systems can gather and process information Digital 1 Analog region Optical response Digital 0 Chemical stimulus level
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 micelle with ion cloud
receptor receptor receptor receptor 1 1 2 2 fluorophore fluorophore anchor anchor spacer spacer spacer spacer + + H H Na Na O O O N O O O O S N 3
and + + H H H H + + Na Na IF none 0 400 400 500 500 Wavelength (nm)
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 Count Date : 20.08.2005 Description Result Units Reference Ranges Remarks Haemoglobin 8.70* g/dl 12.00 17.50 Low RBC 2.34* x 10x6/mm3 3.50 6.00 Low PCV 26.70* % 40.00 54.00 Low MCV 114.10* fl 70.00 96.00 High MCH 37.20 pg 27.00 32.00 High MCHC 32.60 g/dl 30.00 ….35.00 …Normal PLATELETS 140,000.00 mm3 150,000.00 450,000.00 Low WBC 8,200.00 mm3 4,000.00 11,000.00 Normal NEUTROPHILS 48.00 % 40.00 75.00 …normal LYMPHOCYTES48.00 % 10.00 45.00 High EOSINOPHILS 2.0 % 1.00 6.00 Normal MONOCYTES 2.00 % < 10.00 Normal Performed by Sysmex/Hycell Automated Haematology Analyzers Logical combination of ‘high’ and ‘low’ parameters identifies disease
Spacer Receptor Spacer Receptor Receptor + + Na H H 2+ Zn O - O C O 2 O - N C O N O 2 O Spacer Fluorophore
+ + 2+ Na , H , Zn + + Na , H + 2+ Na , Zn + Na IF + 2+ H , Zn 2+ Zn + H No inputs 0 400 440 480 520 Wavelength / nm
3-Input AND Logic Truth Table Input1 Na+ Input2 H+ Input3 Zn2+ Output FluornF 0 (low) 0 (low) 0 (low) 0 (low, 0.001) 0 (low) 1 (high) 0 (low) 0 (low, 0.001) 0 (low) 0 (low) 1 (high) 0 (low, 0.002) 0 (low) 1 (high) 1 (high) 0 (low, 0.003) 1 (high) 0 (low) 0 (low) 0 (low, 0.006) 1 (high) 1 (high) 0 (low) 0 (low, 0.007) 1 (high) 0 (low) 1 (high) 0 (low, 0.006) 1 (high) 1 (high) 1 (high) 1 (high, 0.020)
Molecular Computational Identification (MCID) of Small ObjectsinPopulations 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)
Prefabricated YES logic gate fixed to polymer bead (0.1 mm) 422 100 Increasing pH 401 446 Fluorescence Intensity 0 Wavelength (nm) 500 385 EXCITATION WAVELENGTH:368 nm
Prefabricated logic gates fixed to polymer beads NOT PASS 1 YES O N O N H N H 100 PASS 1 I YES F NOT 0 1 3 5 7 9 11 pH
Arraying gates with identical fluorophores and different logic type 2.5 % loading 2.5 % loading H H N N 422 N 100 O O Increasing pH 446 401 I F 0 385 500 Wavelength (nm)
Input (H+) Output (Fluorescence) Output (Fluorescence) Total Output (Fluorescence) 0 1 0 1 100 80 1 1 1 2 60 Emission (at 422 nm) 40 20 0 2.5 4.5 6.5 8.5 10.5 OUT ( Blue fluorescence) pH IN (H+) OUT ( Blue fluorescence) pKa : 4.4
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 mm objects can be encoded!
A D C B A; PASS 1 B; NOT C; PASS 1 D; PASS 1 + YES (1:1) E; YES F; NOT G; PASS 1 I; YES J; PASS 0 acid E G F I J A D B C alkali E G F I J
“Plug-and-Play” Logic via Self-Assembly Vinny Vance, Catherine Dobbin, Boontana Wannalerse Chem. Commun. 2009, 1386
Covalently bound YES Logic: n - C H 9 1 9 N N Self-Assembled YES Logic: L II Ru N N Assembler: Non-ionic Detergent Micelle n - C H S 9 1 9 2 - O L R R O H O 10 Long-lived (100 ns) lumophore
- O pKa = 9.9
Covalently bound AND Logic: - - C O C O L 2 2 N O n - C H 8 1 7 Self-Assembled AND Logic: S S - O L R1 R1 R2 R2 Log bCa2+ = 1.5 pKa = 9.9 pKa = 5.8
- O - - 11; 10-8 M H+ and 0.2 M Ca2+ C O C O 2 2 01; 10-12 M H+ and 0.2 M Ca2+ N 10; 10-8 M H+ only O 00; 10-12 M H+ only n - C H 8 1 7
Covalently bound OR Logic: - - C O C O 2 2 Non-selective Receptor N L O n - C H 8 1 7 Self-Assembled OR Logic: S binds H+ or Ca2+ L R R pKa = 5.8 Log bCa2+ = 1.5
- - 11; 10-4 M H+ and 0.2 M Ca2+ C O C O 2 2 10; 10-4 M H+ only N 01; 10-8 M H+ and 0.2 M Ca2+ O 00; 10-8 M H+ only n - C H 8 1 7
Logic Gates with Temperature Input Seiichi Uchiyama, Narumi Kawai Kaoru Iwai (Nara Women’s University) J. Am. Chem. Soc. 2004, 126, 3032
O O and Temperature-sensitive co-polymer N H N H N M e 2 O O Co-polymerizable polarity sensor (Emission weakens in water) N N O N S O N M e 2 2
pH 7 IF 0 10 20 30 40 Temperature / C
pH 9 IF pH 8 pH 7 pH 5 ● 0 60 20 40 0 80 Temperature / C
2-Input INHIBIT Logic Truth Table Input1 Temperature Input2 H+ Output Fluorescence 0 (low; 10 C) 0 (low; 10-9 M) 0 (low; 1) 0 (low; 10 C) 0 (low; 1) 1 (high; 10-5 M) 1 (high; 35 C) 0 (low; 10-9 M) 1 (high; 10) 1 (high; 35 C) 1 (high; 10-5 M) 0 (low; 1)
EPSRC DENI EUROPEAN COMMISSION JAPAN SOCIETY FOR THE PROMOTION OF SCIENCE Providence Luck Serendipity