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Published byKarin Bond Modified over 9 years ago
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Design and Applications of Luminescent Sensing Systems
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The Miniature James Bond
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OFF state Spacer h PET Fluorophore Receptor ON state h PET h M+M+ Spacer Fluorophore Receptor The PET design generalized in Colombo/Belfast Chem. Rev. 1997, 97, 1515 Org. Biomol. Chem. 2008, 6, 2468 Analyst 2009, 134, 2385
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Ion-Switchable Fluorescence Spacer M+M+ FluorophoreReceptor Constant Fluorescence Fluorophore SpacerFluorophoreReceptor < 1 nm > 1 nm
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NEt 2 N 2 O N N NH N 2 Fluorescent PET pH Sensors LysoSensor TM Blue and Green (Invitrogen) DAYA RUPASINGHE NIMAL GUNARATNE J. Chem. Soc. Chem. Commun. 1985, 1669
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Fluorescence Intensity 420 500480 400 Wavelength (nm) 440 460 pH 5.5 7.7 8.0 8.3 8.5 8.8 9.1 9.5 10.5
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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 18 m
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‘Off-On’ sensors selective for Na + and K + Jim Tusa, Marc Leiner Hua-Rui He, Mark Mortellaro (Roche) J. Mater. Chem. 2005, 15, 2640
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Disposable Cassette and OPTI Critical Care Analyzer (CCA) Na + K + Ca ++ or Cl - CO 2 O 2 pH tHb 100M USD Cassette sales ambulances, hospitals, GP and vet surgeries
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Robots for Mapping Small Nanospaces Seiichi Uchiyama (University of Tokyo) Kaoru Iwai (Nara Women’s University) Angew. Chem. Int. Ed. 2008, 47, 4667
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A Popular Robot
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A Useful Robot Mars Rover ‘Opportunity’ January 2005 ‘Curiosity’ August 2012
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fluorophore spacer receptor ICT fluorophore spacer receptor HH + fine positioner gross positioner N S OO N O N N H N O OH 10
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450500550600650700750800 0 pH Wavelength (nm) IFIF
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2030 40 7050 60 0 –0.4 –0.8 –1.6 –1.2 20 30 40 80 0 –0.4 –0.8 –1.2 p p 10 0 –0.4 – – – 102040 5060 70 – – –1.2 p Δ p K a ΔK a 80 O OH 10 O OH OH OH O OH Polarity ( ε ) ε )
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Emulating One-way Electron Traffic of Photosynthesis Jialong Liu Inorg. Chim. Acta 2012, 381, 243
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www.nyu.edu/pages/mathmol/modules/photosynthesis/photo.html inside outside membrane
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fluorophore receptor ICT fluorophore spacer receptor spacerspacer’ receptor receptor’ ++ -- O S O O O N H N N O O Me 2 N O -- ++ N H NMe 2 N O O N O -- ++
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0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 246810 12 pH Fluorescence efficiency N H N N O O Me 2 N O -- ++ N H NMe 2 N O O N O -- ++
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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
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RECEPTOR 1 SPACER FLUOROPHORE RECEPTOR 4 SPACER FLUOROPHORE RECEPTOR 3 SPACER FLUOROPHORE RECEPTOR 2 SPACERFLUOROPHORE IFIF pH Parallel processing to produce greatly increased dynamic range
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0 4 2 8 6 10 0 20 60 40 100 80 IFIF pH 390 500 0 Wavelength (nm) IFIF 100
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Sensitive Molecular Thermometers Seiichi Uchiyama, Yuriko Matsumura Kaoru Iwai (Nara Women’s University) J. Mater. Chem. 2005, 15, 2796
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NIPAM NH O * * CONHiPr n Temperature-sensitive polymer O O N SO 2 NMe 2 N O N Co-polymerizable polarity sensor (Emission weakens in water) Increasing temperature Sensor exposed Sensor hidden H2OH2O
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42 C 20 C 500 600 Wavelength (nm) IFIF 0
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Temperature / o C 10 30 50 IFIF 0 10 NH O O NH NH O 1:11:1 1:31:3 3:13:1 1:11:1 1:31:3 3:13:1
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12 ns (33 o C) 4 ns (31 o C) Intensity image Lifetime image 100 m Molecular Thermometry in a small space via FLIM Seiichi Uchiyama (Tokyo), Kaoru Iwai (Nara) Emmelyn Hughes & Anita Jones (Edinburgh) Steven Magennis (Manchester) Lab. Chip 2010, 10, 1267
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Arrival of Twisted Internal Charge Transfer (TICT) States in PET Systems Shuai Zheng, Tom Moody, Mark Lynch, Nimal Gunaratne, Terry Rice Photochem. Photobiol. Sci. 2012, 11, 1675 N O O Bu N Me NM e 2 H n
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N Bu N Me NM e 2 O O. +.- n N O O Bu N Me NM e 2 H n
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440 480 520 560 600 Wavelength / nm 0 Fluorescence Intensity pH = 0.031 = 0.011
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