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Design and Applications of Luminescent Sensing Systems.

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Presentation on theme: "Design and Applications of Luminescent Sensing Systems."— Presentation transcript:

1 Design and Applications of Luminescent Sensing Systems

2 The Miniature James Bond

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4 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

5 Ion-Switchable Fluorescence Spacer M+M+ FluorophoreReceptor Constant Fluorescence Fluorophore SpacerFluorophoreReceptor < 1 nm > 1 nm

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8 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

9 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

10 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

11 ‘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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13 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

14 Robots for Mapping Small Nanospaces Seiichi Uchiyama (University of Tokyo) Kaoru Iwai (Nara Women’s University) Angew. Chem. Int. Ed. 2008, 47, 4667

15 A Popular Robot

16 A Useful Robot Mars Rover ‘Opportunity’ January 2005 ‘Curiosity’ August 2012

17 fluorophore spacer receptor ICT fluorophore spacer receptor HH + fine positioner gross positioner N S OO N O N N H N O OH 10

18 450500550600650700750800 0 pH Wavelength (nm) IFIF

19 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 )

20 Emulating One-way Electron Traffic of Photosynthesis Jialong Liu Inorg. Chim. Acta 2012, 381, 243

21 www.nyu.edu/pages/mathmol/modules/photosynthesis/photo.html inside outside membrane

22 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 -- ++

23 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 -- ++

24 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

25 RECEPTOR 1 SPACER FLUOROPHORE RECEPTOR 4 SPACER FLUOROPHORE RECEPTOR 3 SPACER FLUOROPHORE RECEPTOR 2 SPACERFLUOROPHORE IFIF pH Parallel processing to produce greatly increased dynamic range

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27 0 4 2 8 6 10 0 20 60 40 100 80 IFIF pH 390 500 0 Wavelength (nm) IFIF 100

28 Sensitive Molecular Thermometers Seiichi Uchiyama, Yuriko Matsumura Kaoru Iwai (Nara Women’s University) J. Mater. Chem. 2005, 15, 2796

29 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

30 42 C 20 C 500 600 Wavelength (nm) IFIF 0

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32 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

33 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

34 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

35 N Bu N Me NM e 2 O O. +.- n N O O Bu N Me NM e 2 H n

36 440 480 520 560 600 Wavelength / nm 0 Fluorescence Intensity pH  = 0.031  = 0.011


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