Design and Applications of Luminescent Sensing Systems

The Miniature James Bond

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

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

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

Fluorescence Intensity Wavelength (nm) pH

Cancer cells respond to radiation by developing acidic vesicular organelles. Sensor: Lysosensor Blue Paglin et al (Sloan-Kettering Center, NY) Cancer Res. 2001, 61,  m

‘Off-On’ sensors selective for Na + and K + Jim Tusa, Marc Leiner Hua-Rui He, Mark Mortellaro (Roche) J. Mater. Chem. 2005, 15, 2640

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

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 ‘Curiosity’ August 2012

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

pH Wavelength (nm) IFIF

–0.4 –0.8 –1.6 – –0.4 –0.8 –1.2 p p 10 0 –0.4 – – – – – –1.2 p Δ p K a ΔK a 80 O OH 10 O OH OH OH O OH Polarity ( ε ) ε )

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

inside outside membrane

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 -- ++

pH Fluorescence efficiency N H N N O O Me 2 N O -- ++ N H NMe 2 N O O N O -- ++

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

IFIF pH Wavelength (nm) IFIF 100

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

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

42 C 20 C Wavelength (nm) IFIF 0

Temperature / o C 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

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

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

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

Wavelength / nm 0 Fluorescence Intensity pH  =  = 0.011