Serdar Özçelik

Superradiant lasing from J-aggregated molecules adsorbed onto colloidal silver

The picosecond time-resolved emission spectrum of the cyanine dye 1,1′-diethyl-3,3′bis-(3-sulfopropyl)-5,5′,6,6′-tetrachlorobenzimidazolocarbocyanine (also known as BIC) adsorbed onto colloidal silver was examined as a function of laser pulse energy at room temperature. BIC is found to aggregate on colloidal silver, and the number of coherently responding molecules involved in the one-exciton state (i.e., the coherence length) was estimated to involve 8–9 molecules. Lasing at a remarkably low incident pulse energy threshold was found for this system and explained in terms of a mechanism involving superradiant states created in coherently coupled adsorbed molecules that emit photons which stimulate emission from other spatially distributed superradiant states.

Biofunctional quantum dots as fluorescence probe for cell-specific targeting☆

We describe here the synthesis, characterization, bioconjugation, and application of water-soluble thioglycolic acid TGA-capped CdTe/CdS quantum dots (TGA-QDs) for targeted cellular imaging. Anti-human epidermal growth factor receptor 2 (HER2) antibodies were conjugated to TGA-QDs to target HER2-overexpressing cancer cells. TGA-QDs and TGA-QDs/anti-HER2 bioconjugates were characterized by fluorescence and UV-Vis spectroscopy, X-ray diffraction (XRD), hydrodynamic sizing, electron microscopy, and gel electrophoresis. TGA-QDs and TGA-QDs/anti-HER2 were incubated with cells to examine cytotoxicity, targeting efficiency, and cellular localization. The cytotoxicity of particles was measured using an MTT assay and the no observable adverse effect concentration (NOAEC), 50% inhibitory concentration (IC50), and total lethal concentration (TLC) were calculated. To evaluate localization and targeting efficiency of TGA-QDs with or without antibodies, fluorescence microscopy and flow cytometry were performed. Our results indicate that antibody-conjugated TGA-QDs are well-suited for targeted cellular imaging studies.

Extremely low excitation threshold, superradiant, molecular aggregate lasing system

An extremely low threshold for lasing from a specially formulated system involving self-assembled, aggregated molecules enables the system to function as a mirrorless laser. Superradiant energy states created in coherently coupled aggregated molecules emit photons that stimulate emission from other spatially distributed superradiant states. This study focuses on a cyanine dye (specifically, 1,1′-3,3′-tetraethyl-5,5′,6,6′-tetrachlorobenzimidazolocarbocyanine iodide) adsorbed onto silica colloid on which the dye aggregates, forming excitonic states involving coherent domains in which a finite number of molecules act cooperatively in the process of emitting photons. It is found that lasing from such a system is induced at a threshold of ca. 39 pJ/pulse, which corresponds to a factor of 3×10+4 times smaller than the lowest lasing threshold reported in the literature.

Developing a facile method for highly luminescent colloidal CdSxSe1−x ternary nanoalloys

We report a facile method to synthesize highly luminescent colloidal CdSxSe1−x ternary nanoalloys. The synthesis is achieved exactly in one-step, one-pot and at low temperature, by applying the two-phase thermal approach. The optical and structural properties of the nanoalloys were characterized by various techniques. Photoluminescence of the nanoalloys is tunable from 435 to 545 nm by either the size or the composition of the nanoalloys. Highly luminescent nanoalloys having quantum yields up to 90% were prepared. The hydrodynamic size of the nanoalloys can be varied from 1.4 to 10.0 nm by the reaction time. DLS measurements showed that the size distribution of the nanoalloys is monodispersed. TEM images confirmed the size and the size distribution of the nanoalloys. The sulfur fraction in the nanoalloy composition, measured by XRD and verified by EDX, is modulated from 0.17 to 0.95 by increasing the amount of thiourea in the chalcogenide mixture. The sulfur-rich nanoalloys are formed when the initial mole ratio of the chalcogenide (S : Se) is equal or higher than eleven-fold. The gradient and homogeneous internal structures are revealed by analysis of the alloy composition as a function of the growth time. We propose that the two-phase approach, a non-injection technique, is a facile and versatile method to develop highly luminescent CdSxSe1−x nanoalloys without an inorganic coating layer.

Tuning Photoinduced Intramolecular Electron Transfer by Electron Accepting and Donating Substituents in Oxazolones

The solvatochromic and spectral properties of oxazolone derivatives in various solvents were reported. Fluorescence spectra clearly showed positive and negative solvatochromism depending on substituents. The solvatochromic plots and quantum chemical computations at DFT-B3LYP/6-31 + G(d,p) level were used to assess dipole moment changes between the ground and the first excited singlet-states. The electron accepting nitro substituent at the para-position increased the π-electron mobility, however, the 3,5-dinitro substituent decreased the π-electron mobility as a result of inverse accumulation of the electronic density as compared with that of its ground state. Experimental and computational studies proved that the photoinduced intramolecular electron transfer (PIET) is responsible for the observed solvatochromic effects. We demonstrate that PIET can be finely tailored by the position of the electron accepting and donating substituents in the phenyl ring of the oxazolone derivatives. We propose that the photoactive CPO derivatives are new molecular class of conjugated push-pull structures using azlactone moiety as the π-conjugated linker and may find applications in photovoltaic cells and light emitting diodes.

pH responsive glycopolymer nanoparticles for targeted delivery of anti-cancer drugs

Over the past decade, there has been a great deal of interest in the integration of nanotechnology and carbohydrates. The advances in glyconanotechnology have allowed the creation of different bioactive glyconanostructures for different types of medical applications, especially for drug delivery and release systems. Therefore, the use of more efficient biocompatible nanocarriers with high loading capacity, low overall toxicity and receptor-mediated endocytosis specificity is still in focus for the enhancement of the therapeutic effect. Conjugation of sugar derivatives onto gold nanoparticles presents unique properties that include a wide array of assembling models and size-related electronic, magnetic and optical properties. Here, pH-responsive drug-conjugated glycopolymer-coated gold nanoparticles were prepared by functionalization of gold nanoparticles with thiol-terminated glycopolymers and then subsequent conjugation of doxorubicin (DOX). Among the four different glycopolymers, their drug release, physicochemical characterization (spectroscopy, particle size and surface charge) and in vitro bioapplications with four different cell lines were compared. As a result, pH-sensitive drug delivery via sugar-coated AuNPs was performed thanks to hydrazone linkages between glycopolymers and DOX. Comparative viability tests also demonstrated the efficiency of glycopolymer–DOX conjugates by fluorescence cell imaging. The obtained results reveal that AuNP homoglycopolymer DOX conjugates (P4D) have significant potential, especially in human neuroblastoma cells in comparison to cervical cancer cells and lung cancer cells.

Composites of Reactive Silica Nanoparticles and Poly(glycidyl methacrylate) with Linear and Crosslinked Chains by in situ Bulk Polymerization

Composites of poly(glycidyl methacrylate) (PGMA) and L-lysine-coated silica nanoparticles with varying contents were prepared by in situ bulk polymerization using benzoyl peroxide (BPO) as free radical initiator. Silica nanoparticles covered by L-lysine molecules were synthesized using emulsion method. Dynamic light scattering measurements confirmed that the particles are highly monodisperse with the diameter of 10 nm and free of aggregates in the monomer (glycidyl methacrylate, GMA). Upon polymerization of the homogeneous particle/monomer dispersion, aggregates of individual silica nanoparticles are observed by tapping mode atomic force microscope (AFM). Amine and/or carboxylic acid sites on particle surface covalently react with the oxirane groups of the polymer backbone. The aggregation was substantially suppressed by using a difunctional comonomer divinyl benzene (DVB) in polymerization. A three-dimensional polymer network, P(GMA-DVB), forms throughout the system. This structure leads to significant progress in particle dispersion, therefore in physical properties of the resulting composite. We demonstrated that the composites prepared by crosslinked chains are thermally more stable and mechanically stiffer than those prepared by linear ones.