Table Of ContentTopics in
Fluorescence
Spectroscopy
Volume 9
Advanced Concepts in
Fluorescence Sensing
Part A: Small Molecule Sensing
Topics in Fluorescence Spectroscopy
Edited by JOSEPH R. LAKOWICZ and CHRIS D. GEDDES
Volume 1: Techniques
Volume 2: Principles
Volume 3: Biochemical Applications
Volume 4: Probe Design and Chemical Sensing
Volume 5; Nonlinear and Two-Photon-Induced Fluorescence
Volume 6: Protein Fluorescence
Volume 7: DNA Technology
Volume 8: Radiative Decay Engineering
Volume 9: Advanced Concepts in Fluorescence Sensing
Part A: Small Molecule Sensing
Volume 10: Advanced Concepts in Fluorescence Sensing
Part B: Macromolecular Sensing
Topics in
Fluorescence
Spectroscopy
Volume 9
Advanced Concepts in
Fluorescence Sensing
Part A: Small Molecule Sensing
Edited by
CHRIS D. GEDDES
The Institute of Fluorescence
Medical Biotechnology Center
University of Maryland Biotechnology Institute
Bcdtimore, Maryland
and
JOSEPH R. LAKOWICZ
Center for Fluorescence Spectroscopy and
Department of Biochemistry and Molecular Biology
University of Maryland School of Medicine
Baltimore, Maryland
^ Springer
The Library of Congress cataloged the first volume of this title as follows:
Topics in fluorescence spectroscopy/edited by Chris D. Geddes and Joseph R. Lakowicz.
p. cm.
Includes bibliographical references and index.
Contents: v. 1. Techniques
1. Fluorescence spectroscopy. 1. Geddes, Chris D. II. Lakowicz, Joseph R.
QD96.F56T66 1991 91-32671
543'.0858—dc20 CIP
ISSN: 1574-1036
ISBN 0-387-23334-2 Printed on acid-free paper
©2005 Springer Science+Business Media, Inc.
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CONTRIBUTORS
Joanne M. Bedlek-Anslow, DuPont Nylon, South Carolina.
Paul D. Beer. Inorganic Chemistry Laboratory, Department of Chemistry, University of
Oxford, South Parks Road, Oxford, 0X1 3QR, UK.
Bruce F. Carroll. Department of Mechanical and Aerospace Engineering, University of
Florida, Gainesville, FL, 32611.
David Curiel. Inorganic Chemistry Laboratory, Department of Chemistry, University of
Oxford, South Parks Road, Oxford, OXl 3QR, UK.
Luisa Stella Dolci. Universita degli studi di Bologna, Dipartimento di Chimica "G.
Ciamician", Via Selmi 2, I 40126, Bologna, Italy.
Ute Resch-Genger. Federal Institute for Materials Research and Testing, Richard-
Willstatter-Str. 11, D- 12489 Berlin, Germany.
Elizabeth J. Hayes. Inorganic Chemistry Laboratory, Department of Chemistry,
University of Oxford, South Parks Road, Oxford, 0X1 3QR, UK.
Gunther Hennrich. Dpto. de Quimica Organica, L 101, Facultad de Ciencias, Universidad
Autonoma de Madrid, Cantoblanco 28049-Madrid, Spain.
Stephanie Hodgen. Department of Pure and Applied Chemistry, University of
Strathclyde, Glasgow, Gl IXL, UK
Scott A. Hilderbrand. Department of Chemistry, Massachusetts Institute of Technology,
77 Massachusetts Avenue, Cambridge 02139.
John P. Hubner. Department of Mechanical and Aerospace Engineering, University of
Florida, GainesviUe, FL, 32611
Muhammet E. Kose. Department of Chemistry, University of Florida, Gainesville, FL,
32611.
Kanji Kubo. Kyushu University, Fukuoka, Japan 816-8580.
Mi Hee Lim. Department of Chemistry, Massachusetts Institute of Technology, 77
Massachusetts Avenue, Cambridge, 02139.
CONTRIBUTORS
Stephen J. Lippard. Department of Chemistry, Massachusetts Institute of Technology, 77
Massachusetts Avenue, Cambridge, MA 02139..
Andrew Mills. Department of Pure and Applied Chemistry, University of Strathclyde,
Glasgow, Gl IXL, UK
Marco Montalti. Universita degli studi di Bologna, Dipartimento di Chimica "G.
Ciamician", Via Selmi 2, I 40126, Bologna, Italy.
Luca Prodi. Universita degli studi di Bologna, Dipartimento di Chimica "G. Ciamician",
Via Selmi 2,1 40126, Bologna, Italy.
Kirk S. Schanze. Department of Chemistry, University of Florida, Gainesville, FL, 32611.
Jan W. Verhoeven. Laboratory of Organic Chemistry, University of Amsterdam, Nieuwe
Achtergracht 129, 1018WS Amsterdam, The Netherlands.
Nelsi Zaccheroni. Universita degli studi di Bologna, Dipartimento di Chimica "G.
Ciamician", Via Selmi 2,1 40126, Bologna, Italy.
PREFACE
Over the last decade fluorescence has become the dominant tool in
biotechnology and medical imaging. These exciting advances have been underpinned by
the advances in time-resolved techniques and instrumentation, probe design, chemical /
biochemical sensing, coupled with our furthered knowledge in biology.
Ten years ago Volume 4 of the Topics in Fluorescence Spectroscopy series
outlined the emerging trends in time resolved fluorescence in analytical and clinical
chemistry. These emerging applications of fluorescence were the result of continued
advances in both laser and computer technology and a drive to develop red/near-infrared
fluorophores. Based on the advancements in these technologies, it was envisaged that
small portable devices would find future common place in a doctor's office or for home
health care.
Today, these past emerging trends in fluorescence sensing are now widely used
as either standard practices in clinical assessment or commercialized health care products.
Miniature lasers in the form of laser diodes and even light emitting diodes are widely
used in applications of time-resolved fluorescence. Computer clock-speed is now not
considered a hurdle in data analysis. Even our choice of fluorophores has changed
dramatically in the last decade, the traditional fluorophore finding continued competition
by fluorescent proteins and semi-conductor quantum dots, to name but just a few.
This volume "Advanced Concepts in Fluorescence Sensing: Small Molecule
Sensing" aims to summarize the current state of the art in fluorescence sensing. For this
reason we have invited chapters, encompassing a board range of fluorescence sensing
techniques. Chapters in this volume deal with small molecule sensors, such as for anions,
cations and C02.
While many of the changes in recent fluorescence have been well received, its
continued growth in the world has created a challenge in trying to archive and document
its use. Subsequently Chris D. Geddes has now become co-series editor of the Topics in
Fluorescence Spectroscopy series. We have also recently launched the Reviews in
Fluorescence series, which co-edited also by Dr's Geddes and Lakowicz and pubhshed
annually, is meant to directly compliment the Topics in Fluorescence Spectroscopy
series, with small chapters summarizing the yearly progress in fluorescence.
Finally we would like to thank all the authors for their excellent contributions,
Mary Rosenfeld for administrative support and Kadir Asian for help in typesetting the
volume.
Chris D. Geddes
Joseph R. Lakowicz
Baltimore,Maryland, US.
August 2004
CONTENTS
1. PROBES AND SENSORS FOR CATIONS 1
Luca Prodi, Marco Montalti, Nelsi Zaccheroni, and Luisa Stella Dolci
1.1. INTRODUCTION 1
1.1.1. The Need of Chemical Sensors 1
1.1.2. The Power of Tuminescence Spectroscopy 2
1.1.3. Sensory Devices and Chemosensors; the Role of Chemists 2
1.1.4. Chemosensors and Probes for Metal Ions 5
1.2. CHEMOSENSORS WITH ACYCLIC RECEPTOR 6
1.3. CHEMOSENSORS WITH CYCLIC RECEPTOR 21
1.4. SENSORS WITH DENDRIMER-, PEPTIDE- AND PROTEIN-BASED
RECEPTOR 42
1.5. SENSORS BASED ON SILICA NANOPARTICLES 47
1.6. CONCLUSIONS 51
1.6.1 Acknowledgments 51
1.7. REFERENCES 52
2. FLUORESCENT ANION COMPLEXATION AGENTS 59
David Curiel, Elizabeth J. Hayes and Paul D. Beer
2.1. INTRODUCTION 59
2.2. ORGANIC ANION SENSORS 60
2.2.1. Sensors with Naphthalene as Signalling Unit 60
2.2.2. Sensors with Anthracene as Signalling Unit 66
2.2.3. Sensors with Pyrene as Signalling Unit 79
2.2.4. Sensors with Other Hydrocarbonated Signalling Unit 82
2.2.5. Sensors with Condensed or Conjugated Heteroaromatic Rings as
Signalling Unit 82
2.2. 6. Sensors with Other Fluorescent Probes as Signalling Unit 89
2.3. ESIORGANIC SENSORS FOR ANIONS 94
IX
CONTENTS
2.3.1. Ruthenium (II) - and Rhenium (I)-Bipyridyl-based Receptors 94
2.3.2 Sensors containing other fluorophores 105
2.3.3 Lanthanide-based receptors 108
2.4. REFERENCES 113
3. FLUORESCENT CARBON DIOXIDE INDICATORS 119
Andrew Mills and Stephanie Hodgen
3.1. INTRODUCTION 119
3.2. THE TWO TYPES OF CARBON DIOXIDE OPTICAL SENSOR
SYSTEMS 121
3.2.1 Wet Optical Sensors for Carbon Dioxide 121
3.2.2 Dry Optical Sensors for Carbon Dioxide 137
3.3. APPLICATIONS AND PRACTICAL SYSTEMS 155
3.4. LIST OF TERMS AND SYMBOLS 158
3.5. REFERENCES 159
4. FLUORESCENCE-BASED NITRIC OXIDE DETECTION 163
Scott A. Hilderbrand, Mi Hee Lim, and Stephen J. Lippard*
4.1. INTRODUCTION 163
4.2. CURRENT NON-FLUORESCENT DETECTION METHODS 164
4.3. EARLY FLUOROMETRIC IMAGING OF NO 166
4.4. THE DIAMINOFLUORESCEFN PLATFORM 167
4.5. OTHER o-DIAMINE NO SENSORS 169
4.6. BIOLOGICAL NO DETECTION WITH o-DIAMEs[E-BASED
SENSORS 169
4.7. OTHER ORGANIC SENSORS 171
4.8. TRANSITION METAL SYSTEMS AND FIBER-OPTIC
NO DETECTION 173
4.9. IRON COMPLEXES 174
4.10. COBALT COMPLEXES 176
4.10.1. Cobah SATI Sensors 176
4.10.2. Cobah FATI Sensors 180
4.11. DIRHODIUM TETRACARBOXYLATES AS REVERSIBLE NO
SENSORS 181
4.12. SUMMARY 183
4.13. REFERENCES 184
CONTENTS xi
5. FLUORESCENT REDOX-SWITCHABLE DEVICES 189
Ute Resch-Genger and Gunther Hennrich
5.1. INTRODUCTION 189
5.2. REDOX-ACTIVATED FLUORESCENCE SIGNAL GENERATION 190
5.2.1. Redox-Active Control Units 192
5.2.2. Composite Fluorescent Redox Switches 194
5.2.3. Fluorescence Signalling of Redox-Active Analytes 196
5.3. FLUORESCENT REDOX-ACTIVE AND ANALYTE-RESPONSIVE
DEVICES 199
5.3.1. Fluorosensors with Redox Control of Analyte Recognition and
Fluorescence 202
5.4. CONCLUSION AND OUTLOOK 211
5.5. ACKNOWLEDGEMENT 211
5.6. REFERENCES 211
6. PET SENSORS 219
Kanji Kubo
6.1, INTRODUCTION 219
6.2, PRINCIPLE OF PET SENSORS 220
6.2.1. "OFF-ON" Switches 220
6.2.2. "ON-OFF" Switches 222
6.2.3. "OFF-ON-OFF" Switches 224
6.3, DESIGN OF PET SENSORS 225
6.3.1, Design of the Fluorophore Unit 226
6.3.2, Design of the Spacer Unit 226
6.3.3, Design of the Receptor Unit 226
6.4, CLASSIFICATION OF PET SENSORS 227
6.4.1. Coronand (Crown)-Based PET Sensors 227
6.4.2. Chelator- and Podand-Based PET Sensors 231
6.4.3. Cryptand-Based PET Sensors 236
6.4.4. Cavitand-Based PET Sensors : 238
6.4.5. Polymer-Supported PET Sensors 238
6.4.6. PET Sensors Involving Excimer Formation 239
6.4.7. PET Sensors Involving Energy Transfer 240
6.5, PET SENSORS AS LOGIC GATES 241
6.6, CONCLUSIONS 243
6.7, REFERENCES 243
