Semiconductor Quantum Dots with Photoresponsive Ligands.
Photochromic or photocaged ligands can be anchored to the outer shell of semiconductor quantum dots in order to control the photophysical properties of these inorganic nanocrystals with optical stimulations. One of the two interconvertible states of the photoresponsive ligands can be designed to accept either an electron or energy from the excited quantum dots and quench their luminescence. Under these conditions, the reversible transformations of photochromic ligands or the irreversible cleavage of photocaged counterparts translates into the possibility to switch luminescence with external control. As an alternative to regulating the photophysics of a quantum dot via the photochemistry of its ligands, the photochemistry of the latter can be controlled by relying on the photophysics of the former. The transfer of excitation energy from a quantum dot to a photocaged ligand populates the excited state of the species adsorbed on the nanocrystal to induce a photochemical reaction. This mechanism, in conjunction with the large two-photon absorption cross section of quantum dots, can be exploited to release nitric oxide or to generate singlet oxygen under near-infrared irradiation. Thus, the combination of semiconductor quantum dots and photoresponsive ligands offers the opportunity to assemble nanostructured constructs with specific functions on the basis of electron or energy transfer processes. The photoswitchable luminescence and ability to photoinduce the release of reactive chemicals, associated with the resulting systems, can be particularly valuable in biomedical research and can, ultimately, lead to the realization of imaging probes for diagnostic applications as well as to therapeutic agents for the treatment of cancer.
Laboratory for Molecular Photonics, Department of Chemistry, University of Miami, 1301 Memorial Drive, Coral Gables, FL, 33146-0431, USA.
Lorenzo
L
Sansalone
Laboratory for Molecular Photonics, Department of Chemistry, University of Miami, 1301 Memorial Drive, Coral Gables, FL, 33146-0431, USA.
Sicheng
S
Tang
Laboratory for Molecular Photonics, Department of Chemistry, University of Miami, 1301 Memorial Drive, Coral Gables, FL, 33146-0431, USA.
Yang
Y
Zhang
Laboratory for Molecular Photonics, Department of Chemistry, University of Miami, 1301 Memorial Drive, Coral Gables, FL, 33146-0431, USA.
Ek Raj
ER
Thapaliya
Laboratory for Molecular Photonics, Department of Chemistry, University of Miami, 1301 Memorial Drive, Coral Gables, FL, 33146-0431, USA. fraymo@miami.edu.
Françisco M
FM
Raymo
Laboratory for Molecular Photonics, Department of Chemistry, University of Miami, 1301 Memorial Drive, Coral Gables, FL, 33146-0431, USA. jgarciaamoros@ub.edu.|Grup de Materials Orgànics, Departament de Química Inorgànica I Orgànica (Secció de Química Orgànica), Institut de Nanociència i Nanotecnologia (IN2UB), Universitat de Barcelona, Martí i Franqués 1, 08028, Barcelona, Spain. jgarciaamoros@ub.edu.
Jaume
J
Garcia-Amorós
D001578:Benzopyrans / Q000737:chemistry; D004735:Energy Transfer; D007211:Indoles / Q000737:chemistry; D007259:Infrared Rays; D008024:Ligands; D049449:Luminescence; D009569:Nitric Oxide / Q000737:chemistry; D009574:Nitro Compounds / Q000737:chemistry; D045663:Quantum Dots / Q000737:chemistry*; D011789:Quantum Theory; D012666:Semiconductors
D001578:Benzopyrans; D007211:Indoles; D008024:Ligands; D009574:Nitro Compounds; C088184:spiropyran; D009569:Nitric Oxide
Electron transfer; Energy transfer; Photocages; Photochromism; Quantum dots