Françisco M. Raymo

PROFESSOR, ORGANIC CHEMISTRY

Ph.D., University of Birmingham ( UK ), 1996
Postdoctorate, University of Birmingham ( UK ), 1996–1997
Postdoctorate, University of California , Los Angeles, 1997–1999

E-mail: fraymo@miami.edu

Research in a Nugget

Brief description of research

Publications 2004-Present

Link to our laboratory website: Raymo Group


Research in a Nugget


Brief description of research

Research within the Laboratory for Molecular Photonics is aimed at the identification of valuable strategies to manipulate molecules with photons and photons with molecules on the basis of absorption and emission processes.  The ultimate goal of these fundamental studies is the development of new phenomena and innovative materials for possible applications in biomedical research and information technology.  This experimental program demands the design and synthesis of inorganic nanoparticles, organic compounds and macromolecular constructs, their structural characterization and the investigation of their electrochemical, photochemical and photophysical properties.  In this context, the Laboratory for Molecular Photonics has already developed mechanisms to:
·   perform logic operations with photochromic compounds;
·   sense analytes with chromogenic and luminescent assemblies of inorganic nanoparticles and organic compounds;
·   self-assemble films of electrochromic building blocks on metallic electrodes;
·   design photochromic compounds with fast switching speeds and excellent fatigue resistances.
·   activate the luminescence of biocompatible quantum dots with optical stimulations.
Current research efforts are directed to the design of molecular strategies to overcome diffraction and permit the acquisition of fluorescence images with resolution at the nanometer level.  These fundamental investigations can ultimately lead to valuable analytical tools for the visualization of biological samples at the nanoscale with far-field optics and, therefore, can have a significant impact on biomedical research.  Specifically, the Laboratory for Molecular Photonics is in the process of developing experimental protocols to:

·         switch the emission of fluorescent probes under optical control.


Publications 2004-Present

2012
"Fast Fluorescence Switching within Hydrophilic Supramolecular Assemblies": J. Cusido, M. Battal, E. Deniz, I. Yildiz, S. Sortino, F. M. Raymo, Chem. Eur. J.2012,18, DOI:10.1002/chem.201201184

"Insights on the Isomerization of Photochromic Oxazines from the Excitation Dynamics of BODIPY–Oxazine Dyads": E. Deniz, M. Battal, J. Cusido, S. Sortino, F. M. Raymo, Phys. Chem. Chem. Phys.201214, 10300–10307

"Synthesis and Photoresponsive Behavior of Optically-Active Methacrylic Homopolymers Containing Side-Chain Spiropyran Chromophores": L. Angiolini, T. Benelli, E. Bicciocchi, L. Giorgini, F. M. Raymo, React. Funct. Polym.201272, 469–477

"Photoactivatable Fluorophores for Super-Resolution Imaging Based on Oxazine Auxochromes": E. Deniz, M. Tomasulo, J. Cusido, I. Yildiz, M. Petriella, M. L. Bossi, S. Sortino, F. M. Raymo, J. Phys. Chem. C2012116, 6058−6068

"Photoinduced Enhancement in the Luminescence of Hydrophilic Quantum Dots Coated with Photocleavable Ligands": S. Impellizzeri, B. McCaughan, J. F. Callan, F. M. Raymo, J. Am. Chem. Soc.2012134, 2276–2283

"Synthesis and Properties of Molecular Switches Based on the Opening and Closing of Oxazine Rings": E. Deniz, J. Cusido, S. Swaminathan, M. Battal, S. Impellizzeri, S. Sortino, F. M. Raymo, J. Photochem. Photobiol. A2012, 229, 20–28

2011
"Fast and Stable Photochromic Oxazines for Fluorescence Switching": E. Deniz, M. Tomasulo, J. Cusido, S. Sortino, F. M. Raymo, Langmuir201127, 11773–11783

"Structural and Size Effects on the Spectroscopic and Redox Properties of CdSe Nanocrystals in Solution: the Role of Defect States": M. Amelia, S. Impellizzeri, S. Monaco, I. Yildiz, S. Silvi, F. M. Raymo, A. Credi, ChemPhysChem201112, 2280–2288

"Electron and Energy Transfer Mechanisms for Fluorescence Modulation with Photochromic Switches": T. Benelli, M. Tomasulo, F. M. Raymo, Molecular Switches, Eds.: B. L. Feringa, W. R. Browne, Wiley–VCH, Weinheim, 2011, 697–717

"Photochromic Compounds for Fluorescence Nanoscopy": J. Cusido, E. Deniz, F. M. Raymo, Curr. Phys. Chem.20111, 232–241


"Supramolecular Strategies to Construct Biocompatible and Photoswitchable Fluorescent Assemblies": I. Yildiz, S. Impellizzeri, E. Deniz, B. McCaughan, J. F. Callan, F. M. Raymo, J. Am. Chem. Soc.2011133, 871–879

"Molecular Strategies to Read and Write at the Nanoscale with Far-Field Optics": J. Cusido, S. Impellizzeri, F. M. Raymo, Nanoscale20113, 59–70

"A Photoswitchable Bichromophoric Oxazine with Fast Switching Speeds and Excellent Fatigue Resistance": E. Deniz, S. Impellizzeri, S. Sortino, F. M. Raymo,Can. J. Chem.201189, 110–116

"Redox Properties of CdSe and CdSe–ZnS Quantum Dots in Solution": M. Amelia, T. Avellini, S. Monaco, S. Impellizzeri, I. Yildiz, F. M. Raymo, A. Credi, Pure Appl.Chem.201183, 1–8

2010

"Fluorescence Switching with a Photochromic Auxochrome": E. Deniz, S. Sortino, F. M. Raymo, J. Phys. Chem. Lett.20101, 3506–3509174

"Photoswitchable Fluorescent Dyads Incorporating BODIPY and [1,3]Oxazine Components": E. Deniz, S. Ray, M. Tomasulo, S. Impellizzeri, S. Sortino, F. M. Raymo, J. Phys. Chem. A2010114, 11567–11575

"Microwave-Assisted Synthesis of Symmetric and Asymmetric Viologens": M. Lamberto, E. E. Rastede, J. Decker, F. M. Raymo, Tetrahedron Lett.201051, 5618–5620

"Fluorescence Patterning in Films of a Photoswitchable BODIPY–Spiropyran Dyad": E. Deniz, M. Tomasulo, R. A. DeFazio, B. D. Watson, F. M. Raymo, Phys. Chem. Chem. Phys.201012, 11630–11634

"Anti Proliferative and Anti Cancer Properties of Achyranthes Aspera: Specific Inhibitory Activity Against Pancreatic Cancer Cells": P. R. Subbarayan, M. Sarkar, A. Fernandez, S. Impellizzeri, F. M. Raymo, B. L. Lokeshwar, P. Kumar, R. P. Agarwal, B. Ardalan, J. Ethnopharmacol.2010131, 78–82

"Hydrophilic CdSe–ZnS Core–Shell Quantum Dots with Reactive Functional Groups on Their Surface": I. Yildiz, E. Deniz, B. McCaughan, S. F. Cruickshank, J. F. Callan, F. M. Raymo, Langmuir201026, 11503–11511

"Fast Fluorescence Photoswitching in a BODIPY–Oxazine Dyad with Excellent Fatigue Resistance": E. Deniz, S. Sortino, F. M. Raymo, J. Phys. Chem. Lett.2010,1, 1690–1693

"Structural Implications on the Electrochemical and Spectroscopic Signature of CdSe–ZnS Core–Shell Quantum Dots": S. Impellizzeri, S. Monaco, I. Yildiz, M. Amelia, A. Credi, F. M. Raymo, J. Phys. Chem. C2010114, 7007–7013

"Self-Assembled Monolayers and Multilayers of Electroactive Thiols": I. Yildiz, M. Lamberto, F. M. Raymo, Electrochemistry of Functional Supramolecular Systems, Ed.: P. Ceroni, A. Credi, M. Venturi, Wiley–VCH, Weinheim, 2010, 185–200

"Optical Control of Quantum Dot Luminescence via Photoisomerization of a Surface-Coordinated, Cationic Dithienylethene": Z. Erno, I. Yildiz, B. Gorodetsky, F. M. Raymo, N. R. Branda, Photochem. Photobiol. Sci.20109, 249–253

"Hydrophilic and Photochromic Switches Based on the Opening and Closing of [1,3]Oxazine Rings": M. Tomasulo, E. Deniz, S. Sortino, F. M. Raymo, Photochem. Photobiol. Sci.20109, 136–140

"Self-Assembling Films of Chiral Bipyridinium Bisthiols": M. Lamberto, I. Yildiz, S. Sortino, F. M. Raymo, J. Mater. Chem.201020, 981–989

2009

"Photochromic Polymers Based on the Photoinduced Opening and Thermal Closing of [1,3]Oxazine Rings": M. Tomasulo, E. Deniz, T. Benelli, S. Sortino, F. M. Raymo,Adv. Funct. Mater.2009, 19, 3956–3961

"Optical and Chiroptical Switches Based on Photoinduced Photon and Proton Transfer in Copolymers Containing Spiropyran and Azopyridine Chromophores in Their Side Chains": L. Angiolini, T. Benelli, L. Giorgini, F. M. Raymo, Polymer,2009, 50, 5638–5646

"Photochromic Oxazines with Extended Conjugation": M. Åxman Petersen, E. Deniz, M. Brøndsted Nielsen, S. Sortino, F. M. Raymo, Eur. J. Org. Chem.2009, 4333–4339

"Fluorescence Modulation with Photochromic Switches in Nanostructured Constructs": I. Yildiz, E. Deniz, F. M. Raymo, Chem. Soc. Rev.2009, 38, 1859–1867

"Biocompatible CdSe–ZnS Core–Shell Quantum Dots Coated with Hydrophilic Polythiols": I. Yildiz, B. McCaughan, S. F. Cruickshank, J. F. Callan, F. M. Raymo,Langmuir2009, 25, 7090–7096

"Substituent Effects on the Photochromism of Bichromophoric Oxazines": E. Deniz, M. Tomasulo, S. Sortino, F. M. Raymo, J. Phys. Chem. C2009, 113, 8491–8497

"Absorption Spectra of 4-Nitrophenolate Ions measured in Vacuo and in Solution": M.-B. S. Kirketerp, M. Åxman Petersen, M. Wanko, L. Andres Espinosa Leal, H. Zettergren, F. M. Raymo, A. Rubio, M. Brøndsted Nielsen, S. Brøndsted Nielsen,ChemPhysChem, 2009, 10, 1207–1209

"Fluorescent Switches Based on Photochromic Compounds": J. Cusido, E. Deniz, F. M. Raymo, Eur. J. Org. Chem., 2009, 2031–2045

"Photochemical Switching of Luminescence and Singlet Oxygen Generation by Chemical Signal Communication": S. Silvi, E. C. Constable, C. E. Housecroft, J. E. Beves, E. L. Dunphy, M. Tomasulo, F. M. Raymo, A. Credi, Chem. Commun., 2009, 1484–1486

"All-Optical Integrated Logic Operations Based on Chemical Communication between Molecular Switches": S. Silvi, E. C. Constable, C. E. Housecroft, J. E. Beves, E. L. Dunphy, M. Tomasulo, F. M. Raymo, A. Credi, Chem. Eur. J., 2009, 15, 178–185

2008

"
Electron and Energy Transfer Mechanisms to Switch the Luminescence of Semiconductor Quantum Dots": I. Yildiz, M. Tomasulo, F. M. Raymo, J. Mater. Chem.200818, 5577–5584

"A New Family of Photochromic Compounds Based on the Photoinduced Opening and Thermal Closing of [1,3]Oxazine Rings": M. Tomasulo, S. Sortino, F. M. Raymo,J. Photochem. Photobiol. A2008200, 44–49

"Chiroptical Switching Based on Photoinduced Proton Transfer of between Homopolymers Bearing Side-Chain Spiropyran and Azopyridine Moieties": L. Angiolini, T. Benelli, L. Giorgini, F. M. Raymo, Macromol. Chem. Phys.2008209, 2049–2060

"Dithiolane Ligands for Semiconductor Quantum Dots": I. Yildiz, S. Ray, T. Benelli, F. M. Raymo, J. Mater. Chem.200818, 3940–3947

"Photoswitchable Fluorescent Assemblies Based on Hydrophilic BODIPY–Spiropyran Conjugates": M. Tomasulo, E. Deniz, R. J. Alvarado, F. M. Raymo, J. Phys. Chem. C2008112, 8038–8045

"Luminescence Quenching in Supramolecular Assemblies of Quantum Dots and Bipyridinium Dications": B. Gadenne, I. Yildiz, M. Amelia, F. Ciesa, A. Secchi, A. Arduini, A. Credi, F. M. Raymo, J. Mater. Chem.200818, 2022–2027

"Amplification of the Coloration Efficiency of Photochromic Oxazines": M. Tomasulo, S. Sortino, F. M. Raymo, Adv. Mater.200820, 832–835

"Bichromophoric Photochromes Based on the Opening and Closing of a Single Oxazine Ring": M. Tomasulo, S. Sortino, F. M. Raymo, J. Org. Chem.200873, 118–126

2007

"Fluorescence Resonance Energy Transfer in Quantum Dot–Protein Kinase Assemblies": I. Yildiz, X. Gao, T. K. Harris, F. M. Raymo, J. Biomed. Biotechnol.,200718081, 1–5

"Fast and Stable Photochromic Switches Based on the Opening and Closing of [1,3]Oxazine Rings": M. Tomasulo, S. Sortino, F. M. Raymo, Asian Chem. Lett.,200711, 219–222

"A Simple Molecular Machine Operated by Photoinduced Proton Transfer": S. Silvi, A. Arduini, A. Pochini, A. Secchi, M. Tomasulo, F. M. Raymo, M. Baroncini, A. Credi, J. Am. Chem. Soc.2007129, 13378–13379

"Luminescent Chemosensors Based on Semiconductor Quantum Dots": F. M. Raymo, I. Yildiz, Phys. Chem. Chem. Phys.20079, 2036–2043

"Electroactive Films of Multicomponent Building Blocks": I. Yildiz, J. Mukherjee, M. Tomasulo, F. M. Raymo, Adv. Funct. Mater.200717, 814–820

"Synthesis and Properties of Benzophenone–Spiropyran and Naphthalene–Spiropyran Conjugates": M. Tomasulo, S. L. Kaanumal, S. Sortino, F. M. Raymo, J. Org. Chem.200772, 595–605

"Nanoparticle-Induced Transition from Positive to Negative Photochromism": M. Tomasulo, I. Yildiz, F. M. Raymo, Inorg. Chim. Acta2007360, 938–944

"Oxidation of Aqueous EDTA and Associated Organics and Coprecipitation of Inorganics by Ambient Iron-Mediated Aeration": J. D. Englehardt, D. E. Meeroff, L. Echegoyen, Y. Deng, F. M. Raymo, T. Shibata, Env. Sci. Tech. 200741, 270–276
              
2006

"A pH-Sensitive Ligand for Luminescent Quantum Dots": M. Tomasulo, I. Yildiz, S. L. Kaanumalle, F. M. Raymo, Langmuir200622, 10284–10290

"Self-Assembling and Electrochromic Films of Bipyridinium Building Blocks": S. Sortino, S. Conoci, I. Yildiz, M. Tomasulo, F. M. Raymo, J. Mater. Chem.200616, 3171–3173

"Intermolecular Coupling of Motion under Photochemical Control": F. M. Raymo,Angew. Chem. Int. Ed. 200645, 5249–5251

"A Mechanism to Signal Receptor–Substrate Interactions with Luminescent Quantum Dots": I. Yildiz, M. Tomasulo, F. M. Raymo, Proc. Natl. Acad. Sci. USA,2006103, 11457–11460

"Optically-Transparent Ultrathin Pt Films as Versatile Metal Substrates for Molecular Optoelectronics": S. Conoci, S. Petralia, P. Samorì, F. M. Raymo, S. Di Bella, S. Sortino, Adv. Funct. Mater.200616, 1425–1432

"Optical Processing with Photochromic Switches": F. M. Raymo, M. Tomasulo,Chem. Eur. J.200612, 3186–3193

"A Multistate Ensemble of Molecular Switches": S. Sortino, S. Petralia, S. Di Bella, M. Tomasulo, F. M. Raymo, New J. Chem.200630, 515–517

"Luminescence Modulation with Semiconductor Quantum Dots and Photochromic Ligands": M. Tomasulo, I. Yildiz, F. M. Raymo, Aust. J. Chem.200659, 175–178

"Photochromic Nanocomposites of Bipyridinium Dications and Semiconductor Quantum Dots": I. Yildiz, F. M. Raymo, J. Mater. Chem.200616, 1118–1120

"pH-Sensitive Quantum Dots": M. Tomasulo, I. Yildiz, F. M. Raymo, J. Phys. Chem. B2006110, 3853–3855

"A Simple Atomic Force Microscopy Method for the Visualization of Polar and Non-Polar Parts in Thin Organic Films": A. A. Yu, P. R. Stone, J. E. Norville, M. Vaughn, E. J. Pacsial, B. D. Bruce, M. Baldo, F. M. Raymo, F. Stellacci, J. Exp. Nanosci.20061, 63–73

"Chromogenic Oxazines for Cyanide Detection": M. Tomasulo, S. Sortino, A. J. P. White, F. M. Raymo, J. Org. Chem.200671, 744–753

2005

"Supramolecular Assembly of 2,7-Dimethyldiazapyrenium and Cucurbit[8]uril: A New Fluorescent Host for Detection of Catechol and Dopamine": V. Sindelar, M. A. Cejas, F. M. Raymo, W. Chen, S. E. Parker, A. E. Kaifer, Chem. Eur. J.200511, 7054–7059

"Colorimetric Detection of Cyanide with a Chromogenic Oxazine": M. Tomasulo, F. M. Raymo, Org. Lett.20057, 4633–4636

"Optical Writing and Reading with Bilayer Assemblies of Photosensitive and Fluorescent Films": M. Tomasulo, F. M. Raymo, J. Mater. Chem.200515, 4354–4360

"Fast and Stable Photochromic Oxazines": M. Tomasulo, S. Sortino, A. J. P. White, F. M. Raymo, J. Org. Chem.200570, 8180–8189

"Fluorescence Modulation with Photochromic Switches": F. M. Raymo, M. Tomasulo, J. Phys. Chem. A2005109, 7343–7352

"Self-Assembly of Naphthalene Diimides into Cylindrical Microstructures": M. Tomasulo, D. M. Naistat, A. J. P. White, D. J. Williams, F. M. Raymo, Tetrahedron Lett.200546, 5695–5698

"Fluorescent Diazapyrenium Films and Their Response to Dopamine": M. A. Cejas, F. M. Raymo, Langmuir200521, 5795–5802

"Electrochemical Switching of Chromogenic Monolayers Self-Assembled on Transparent Platinum Electrodes": S. Sortino, S. Di Bella, S. Conoci, S. Petralia, M. Tomasulo, E. J. Pacsial, F. M. Raymo, Adv. Mater.200517, 1390–1393

"Fluorescence Modulation in Polymer Bilayers Containing Fluorescent and Photochromic Dopants": M. Tomasulo, S. Giordani, F. M. Raymo, Adv. Funct. Mater.200515, 787–794

"Self-Assembling Bipyridinium Multilayers": R. J. Alvarado, J. Mukherjee, E. J. Pacsial, D. Alexander, F. M. Raymo, J. Phys. Chem. B2005109, 6164–6173

"Electron and Energy Transfer Modulation with Photochromic Switches": F. M. Raymo, M. Tomasulo, Chem. Soc. Rev.200534, 327–336

"A Fast and Stable Photochromic Switch Based on the Opening and Closing of an Oxazine Ring": M. Tomasulo, S. Sortino, F. M. Raymo, Org. Lett.20057, 1109–1112

"Tight Inclusion Complexation of 2,7-Dimethyldiazapyrenium in Cucurbit[7]uril": V. Sindelar, M. A. Cejas, F. M. Raymo, A. E. Kaifer, New J. Chem.200529, 280–282

2004

"Donor/Acceptor Interactions in Self-Assembled Monolayers and Their Consequences on Interfacial Electron Transfer": E. J. Pacsial, D. Alexander, R. J. Alvarado, M. Tomasulo, F. M. Raymo, J. Phys. Chem. B2004108, 19307–19313

"Photoinduced Proton Exchange between Molecular Switches": S. Giordani, M. A. Cejas, F. M. Raymo, Tetrahedron200460, 10973–10981

"Electron Transport in Bipyridinium Films": F. M. Raymo, R. J. Alvarado, Chem. Rec.20044, 204–218

"Intermolecular Fluorescence Modulation: A Mechanism to Process Optical Signals with Molecules": F. M. Raymo, Spectrum200417, 14–18

"Electron Transport in Self-Assembled Bipyridinium Multilayers": F. M. Raymo, R. J. Alvarado, E. J. Pacsial, D. Alexander, J. Phys. Chem. B2004108, 8622–8625

"Molecular Logic Gates": F. M. Raymo, S. Giordani, Encyclopedia of Nanoscience and Nanotechnology, Ed.: H. S. Nalwa, American Scientific Publishers, San Diego,20045, 677–692

"Nanomaterials Synthesis and Applications: Molecule-Based Devices": F. M. Raymo,Handbook of Nanotechnology, Ed.: B. Bhushan, Springer-Verlag, Heidelberg,2004, 9–38