Improved imaging and preservation of lysosome dynamics using silver nanoparticle-enhanced fluorescence.

The dynamics of living cells can be studied by live-cell fluorescence microscopy. However, this requires the use of excessive light energy to obtain good signal-to-noise ratio, which can then photobleach fluorochromes, and more worrisomely, lead to phototoxicity. Upon light excitation, noble metal nanoparticles such as silver nanoparticles (AgNPs) generate plasmons, which can then amplify excitation in direct proximity of the nanoparticle's surface and couple to the oscillating dipole of nearby radiating fluorophores, modifying their rate of emission and thus, enhancing their fluorescence.

Optical writing and single molecule reading of photoactivatable and silver nanoparticle-enhanced fluorescence.

We designed a hybrid nanoparticle-molecular system composed of silver nanostructures (AgNP) and a fluorogenic boron dipyrromethene (BODIPY) that can be selectively activated by UVA or UVC light in the presence of an appropriate photoacid generator (PAG). Light irradiation of the PAG encourages the release of -toluenesulfonic, triflic or hydrobromic acid, any of which facilitate optical 'writing' by promoting the formation of a fluorescent species. Metal-enhanced fluorescence (MEF) by AgNP was achieved through rational design of the nano-molecular system in accordance with the principles of radiative decay engineering.

Two-Photon Excitation of a Plasmonic Nanoswitch Monitored by Single-Molecule Fluorescence Microscopy.

Visible-light excitation of the surface plasmon band of silver nanoplates can effectively localize and concentrate the incident electromagnetic field enhancing the photochemical performance of organic molecules. Herein, the first single-molecule study of the plasmon-assisted isomerization of a photochrome-fluorophore dyad, designed to switch between a nonfluorescent and a fluorescent state in response to the photochromic transformation, is reported. The photochemistry of the switchable assembly, consisting of a photochromic benzooxazine chemically conjugated to a coumarin moiety, is examined in real time with total internal reflection fluorescence microscopy in the presence of silver nanoplates excited with a 633 nm laser.

Dye synthesis in the Pechmann reaction: catalytic behaviour of samarium oxide nanoparticles studied using single molecule fluorescence microscopy.

Photochemically prepared samarium oxide nanoparticles (SmONP) efficiently catalyze the formation of coumarin 153 the Pechmann trans-esterification and condensation process. The formation of the fluorescent coumarin allowed the catalytic process to be monitored in real time at the single molecule level using Total Internal Reflection Fluorescence Microscopy (TIRFM). Benchtop experiments conducted in parallel demonstrated that the observed catalysis occurred in solution rather than by pure heterogeneous catalysis and is due to a mobile population of small SmONP released from a polydisperse original sample containing larger particles.

Sensitized excited free-radical processes as read-write tools: impact on non-linear lithographic processes.

A prefluorescent radical probe in which a 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) unit is sensitized with visible light via energy transfer from a tethered coumarin dye has been synthesized. The excited TEMPO moiety undergoes hydrogen abstraction from a polymer with concomitant functionalization of the polymeric matrix; this writing process can be reversed thermally. The fluorescent probes can be bleached under high intensity illumination, making these new materials suitable for dual-tone lithography with potential applications in sub-diffraction lithographic imaging.

Photoinduced enhancement in the luminescence of hydrophilic quantum dots coated with photocleavable ligands.

In search of strategies to photoactivate the luminescence of semiconductor quantum dots, we devised a synthetic approach to attach photocleavable 2-nitrobenzyl groups to CdSe-ZnS core-shell quantum dots coated with hydrophilic polymeric ligands. The emission intensity of the resulting nanostructured constructs increases by more than 60% with the photolysis of the 2-nitrobenzyl appendages. Indeed, the photoinduced separation of the organic chromophores from the inorganic nanoparticles suppresses an electron-transfer pathway from the latter to the former and is mostly responsible for the luminescence enhancement.

Structural and size effects on the spectroscopic and redox properties of CdSe nanocrystals in solution: the role of defect states.

Two series of CdSe quantum dots (QDs) with different diameters are prepared, according to frequently used protocols of the same synthetic procedure. For each sample the photophysical properties and the potentials for the first reduction and oxidation processes in organic solution are determined. The band gap obtained from electrochemical experiments is compared with that determined from the absorption and luminescence spectra.

Supramolecular strategies to construct biocompatible and photoswitchable fluorescent assemblies.

We designed and synthesized an amphiphilic copolymer with pendant hydrophobic decyl and hydrophilic poly(ethylene glycol) chains along a common poly(methacrylate) backbone. This macromolecular construct captures hydrophobic boron dipyrromethene fluorophores and hydrophobic spiropyran photochromes and transfers mixtures of both components in aqueous environments. Within the resulting hydrophilic supramolecular assemblies, the spiropyran components retain their photochemical properties and switch reversibly to the corresponding merocyanine isomers upon ultraviolet illumination.

Photoswitchable fluorescent dyads incorporating BODIPY and [1,3]oxazine components.

We designed and synthesized three compounds incorporating a BODIPY fluorophore and an oxazine photochrome within the same molecular skeleton and differing in the nature of the linker bridging the two functional components. The [1,3]oxazine ring of the photochrome opens in less than 6 ns upon laser excitation in two of the three fluorophore-photochrome dyads. This process generates a 3H-indolium cation with a quantum yield of 0.

Molecular strategies to read and write at the nanoscale with far-field optics.

Diffraction prevents the focusing of ultraviolet and visible radiations within nanoscaled volumes and, as a result, the imaging and patterning of nanostructures with conventional far-field illumination. Specifically, the irradiation of a fluorescent or photosensitive material with focused light results in the simultaneous excitation of multiple chromophores distributed over a large area, relative to the dimensions of single molecules. It follows that the spatial control of fluorescence and photochemical reactions with molecular precision is impossible with conventional illumination configurations.

Anti-proliferative and anti-cancer properties of Achyranthes aspera: specific inhibitory activity against pancreatic cancer cells.

Aims Of The Study: Achyranthes aspera (Family: Amaranthacea) is a medicinal plant used as an anti-cancer agent in ayurveda, a traditional system of medicine practiced in subcontinental India. The aim of the study was to systematically investigate the anti-proliferative properties of Achyranthes aspera leaves extracted in methanol (LE) on human cancer cells in vitro.

Materials And Methods: We tested time, dose dependent and specific anti-proliferative activity of LE by clonogenic cell survival assay on human cancer and normal epithelial cell lines in vitro.

A redox-driven multicomponent molecular shuttle.

A multicomponent [2]rotaxane designed to operate as a molecular shuttle driven by light energy has been constructed, and its properties have been investigated. The system is composed of (1) a light-fueled power station, capable of using the photon energy to create a charge-separated state, and (2) a mechanical switch, capable of utilizing such a photochemically generated driving force to bring about controllable molecular shuttling motions. The light-fueled power station is, in turn, a dyad comprising (i) a pi-electron-accepting fullerene (C60) component and (ii) a light-harvesting porphyrin (P) unit which acts as an electron donor in the excited state.