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Engineered silica nanoparticles (SiNP) are emerging materials for medical applications. Evaluating biological responses of specific cells treated with engineered silica nanoparticles is however essential. We synthesized and characterized the physicochemical properties of silica nanoparticles with two different sizes of 10 and 100 nm (10SiNP and 100SiNP) dispersed in cell culture medium. HuH-7, an epithelial-like human hepatoblastoma cell line and SK-HEP-1, a liver sinusoidal endothelial cell line (LSEC) are employed to evaluate their biological responses for the SiNP treatment. Primary human lymphocytes are used to assess genotoxicity recommended by OECD guidelines while erythrocytes are used to assess hemolytic activity. The engineered silica nanoparticles are not able to produce radical species, to alter the mitochondrial membrane potential, and induce any adverse effects on cell proliferation. The colony formation ability of HuH-7 hepatoblastoma cells was not affected following the SiNP treatment. Furthermore, SiNPs do not induce hemolysis of red blood cells and are not genotoxic. These findings suggest that SiNPs regardless of the size, amount, and incubation time are biologically safe vehicles to deliver drugs or genes to the liver. © 2020 Elsevier B.V., İzmir Yüksek Teknoloji Enstitüsü, İYTE: 2012IYTEBAP06, This work was supported by the Izmir Institute of Technology [grant number 2012IYTEBAP06 ].

CdSe0.75S0.25 nanoalloys were blended with asymmetric triblock copolymer of polystyrene-b-polyisoprene-b-polystyrene(PS-SIS) in tetrahydrofuran. The fraction of styrene block varies from 14 to 22% with respect to isoprene by mass. The morphology of the copolymer cast film experiences a phase change from cylinder to lamella. CdSe0.75S0.25 nanoalloys were prepared by two-phase method. The surface of the nanoalloys was capped by either oleic acid (OA) or n-tri-octylphosphonic acid (TOPO) in situ. The mean diameter of the alloyed particles is around 12 nm in both systems. The chemical nature of the nanoalloy surface was found to influence the dispersion of the particles over polymer volume. The size of the nanoalloy domains in PS is 50 nm, on average, consisting of approximately 0.7 wt% nanoalloys. However, the size of the nanoalloy domains is smaller when they are loaded into PS-SIS. The structure formation is predominantly determined by enthalpic compatibilization. Atomic force microscopy results suggest that the nanoalloys capped with TOPO sequester into PS-rich domains and enlarge the domain. On the other hand, the ones capped with OA prefer to locate in polyisoprene domains. The increase of particles over 1.0 wt% distorts the lamella structure., Turkish Academy of Sciences (TUBA-GEBiP)

We report molecular aggregate formation of TTBC (1,1′,3,3′- tetraethyl-5,5′,6,6′-tetrachlorobenzimidazolocarbocyanine) in submicrometer-sized PVA (poly(vinyl alcohol)) fibers by electrospinning. The formation of the molecular aggregate is examined by solution and instrumental parameters of electrospinning. The precursor solution of PVA/TTBC, in the range of 0.016-0.065 wt % is subjected to electrospinning under an electrical field ranging from 0.95 to 1.81 kV cm-1. Both randomly deposited and uniaxially aligned fibers are achieved by using two parallel-positioned metal strips as counter electrode. Photoluminescence and polarized Fourier transform infrared spectroscopies are employed to determine spectral properties of the fibers. H-aggregates are formed within the electrospun fibers, regardless of their alignment, and H- and J-type aggregates coexist in the alternative spin-coated and the cast films. A strongly polarized photoluminescence emission is observed in the direction of uniaxially aligned fibers as a result of the orientation of the H-aggregates along the fiber axis. We demonstrate that electrospinning is a process capable of forming and orienting TTBC aggregates during the structural development of the polymer/dye nanofibers. These fibrous films may potentially find applications in optics and electronics., TÜBİTAK TBAG-107T795

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 pi-electron mobility, however, the 3,5-dinitro substituent decreased the pi-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 pi-conjugated linker and may find applications in photovoltaic cells and light emitting diodes.

Spherical silica nanoparticles of various particle sizes (∼10 to 100 nm), produced by a modified Stoeber method employing amino acids as catalysts, are investigated using Dynamic Nuclear Polarization (DNP) enhanced Nuclear Magnetic Resonance (NMR) spectroscopy. This study includes ultra-sensitive detection of surface-bound amino acids and their supramolecular organization in trace amounts, exploiting the increase in NMR sensitivity of up to three orders of magnitude via DNP. Moreover, the nature of the silicon nuclei on the surface and the bulk silicon nuclei in the core (sub-surface) is characterized at atomic resolution. Thereby, we obtain unique insights into the surface chemistry of these nanoparticles, which might result in improving their rational design as required for promising applications, e.g. as catalysts or imaging contrast agents. The non-covalent binding of amino acids to surfaces was determined which shows that the amino acids not just function as catalysts but become incorporated into the nanoparticles during the formation process. As a result only three distinct Q-types of silica signals were observed from surface and core regions. We observed dramatic changes of DNP enhancements as a function of particle size, and very small particles (which suit in vivo applications better) were hyperpolarized with the best efficiency. Nearly one order of magnitude larger DNP enhancement was observed for nanoparticles with 13 nm size compared to particles with 100 nm size. We determined an approximate DNP penetration-depth (∼4.2 or ∼5.7 nm) for the polarization transfer from electrons to the nuclei of the spherical nanoparticles. Faster DNP polarization buildup was observed for larger nanoparticles. Efficient hyperpolarization of such nanoparticles, as achieved in this work, can be utilized in applications such as magnetic resonance imaging (MRI)., Deutsche Forschungsgemeinschaft of the DIP program; Deutsche Forschungsgemeinschaft (DFG); State Planning Organization

In this study, poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] end capped with polyhedral oligomeric silsesquioxanes (MEH-PPV-POSS): cadmium sulfide selenide quantum dots (CdS0.75Se0.25 QDs) nanocomposites based OLEDs were fabricated. By the addition of CdS0.75Se0.25QDs into the polymer active layer, a considerable enhancement was observed in terms of hole and electron injection in devices. Additionally, the presence of QDs reduced the interchain interaction of polymer that resulted in narrower electroluminescence (EL) spectrum. The device structure of ITO/PEDOT: PSS/MEH-PPV-POSS: 25 wt% CdS0.75Se0.25/Ca (40 nm)/Al demonstrated the best performance with a brightness of 8672 cd/m 2 at 10 V, current efficiency of 2.5 cd/A at 8 V, and an EQE of 0.55% at 150 mA/cm2 .

We report a facile method for systematic tuning the hydrodynamic diameter of uniformed fluorescent silica particles in the size range from 12 to 465 nm. Dynamic light scattering and electron microscopy studies demonstrate that the hydrodynamic size distribution of the silica particles is uniform. We show that the initial amounts of ethanol and ammonia are essential to tune the size of these particles. The hydrodynamic diameter of such a particle increases as the amount of ammonia is increased. On the other hand, an increase in the amount of ethanol leads to the formation of smaller particles. Higher initial amount of ethanol yield an increase in the concentration of ethoxide ions and a decrease in the concentration of hydroxide ions. Such control over the concentration of hydroxide ion, which is responsible for the formation of siloxane bonds, causes a controlled-growth of the silica particles, resulting in precise tuning the hydrodynamic size. We confirm that a linear relationship exists between size and brightness of particles, demonstrating that the amount of dye molecules in such particles can be regulated by the presented method. We prove that the silica network provides protection for dye molecules encapsulated in particles against solvents, fluorescence quenchers, and unfavorable pH of environments. Moreover, the fluorescent silica particles with the size of 12, 50 and 250 nm were found to not be cytotoxic against the epithelial cell lines of MCF7 and PC3 even when the dosage levels up to 1.0 mg/ml and incubation periods up to 72 hours were applied.

Microwave-assisted synthesis, photophysical and electrochemical properties of thermal-stable naphthalene benzimidazoles and naphthalimides are studied in this paper. Microwave-assisted synthesis of naphthalene benzimidazoles provide higher yields than the conventional thermal synthesis. Comparative photophysical properties of naphthalene benzimidazoles and naphthalimides are revealed that conjugation of electron-donating group onto naphthalimide moiety increases fluorescence quantum yields. Fluorophore-solvent interactions are also investigated using Lippert-Mataga equation for naphthalimides and naphthalene benzimidazoles. Thermal stabilities of naphthalene benzimidazoles are better than naphthalimides due to increased aromaticity. The experimental E(LUMO) levels of naphthalene benzimidazoles are found to be between 3.15 and 3.28 eV. Therefore, naphthalene benzimidazole derivatives consisting of anchoring groups are promising materials in organic dye sensitized solar cells.

The structure–spectroscopy–function relationship of 1,1′,3,3′-tetraethyl-5,5′,6,6′-tetrachlorobenzimidazolocarbocyanine (TTBC) aggregates is studied using a combination of experimental and theoretical techniques. The aggregates are macroscopically aligned in poly-vinyl-alcohol thin films by vertical spin coating. Angular dependence of the UV–Vis spectra is measured at eleven different orientations between the electric field polarization and the macroscopic alignment axis. The aggregates are characterized by a pair of Davydov split bands with opposite polarization behaviors: an H-band (505 nm) and a J-band (594 nm) polarized respectively, close to being parallel and perpendicular to the alignment axis. Spectral response is interpreted via simulations within the Frenkel exciton formalism. TTBC aggregates are shown to assume very similar internal molecular packing (herringbone) and dynamics of excited states (phonon-assisted intraband and interband relaxations) in ionic aqueous solution and in thin films. The general conclusions on the structure–spectroscopy–function relationship are expected to hold for other cyanine aggregates with the same generic spectral features.

Proceedings of the 16th International Conference on Dynamical Processes in Excited States of Solids, We argued against the current spectral assignment for absorption spectrum of monomeric PIC which is widely accepted since the pioneering works of Scheibe and Jelley [G. Scheibe, Angew. Chem. 49 (1936) 563; E.E. Jelly, Nature 138 (1936) 1009]. A new spectrum is presented along with its conceptual basis. The hypothesized spectrum attributes the previous 0-0 (≈525 nm) and 0-1 (≈490 nm) assignments, respectively, to intermediates acting as the precursor of J-aggregates and to the 0-0 transition of monomeric PIC and brings the spectrum in accord with the seemingly universal spectral fingerprint of cyanines. The hypothesis is used to analyze and interpret the temperature dependence of the UV-vis absorption of PIC aggregates in saline aqueous solution by incorporating the J-band simulations within frenkel exciton formalism. Its implications for aggregate formation kinetics are given on the basis of current spectroscopic evidence. The hypothesis readily answers several long-standing questions: Why compared to many other cyanines at least an order of magnitude higher dye concentration is needed to form J-aggregates of PIC? Why are there no precursors, since aggregation is expected to be a consecutive process? A large number of observations on steady-state and time-resolved spectral properties, and aggregation kinetics in solution/thin films are likely to find reasonable explanations within this hypothesis.

Cataloged from PDF version of article. We report the steady-state and the excited state properties of 1, 3, 1', 3' -tetraethyl-5, 6, 5', 6' -tetrachlorobenzimidazolocarbocyanine iodide (TTBC) in various solvents. The magnitude of the Stokes shift and the average transition energy proves that the structure of the fluorescent state should be very similar to that of the ground-state structure. The fluorescence lifetimes and quantum yields indicate that non-radiative processes are collectively much more effective than the radiative processes. It is therefore suggested that the non-radiative processes, which are driven by the medium around the TTBC molecule control the excited state dynamics. r 2002 Elsevier Science B.V. All rights reserved.

Emission lifetime and steady-state spectral measurements of aggregated and monomeric 3,3′-diethyl-5,5′-dichloro-9-phenylthiacarbocyanine (DDPT) in methanol and aqueous solutions at room temperature have been conducted. We deduce that in aqueous solution DDPT molecules that maintain their monomer emission lifetime and spectral properties exist intimately with molecules that are coherently interconnected in the excitonic structure. Simultaneous superradiance and monomer fluorescence from DDPT molecules occur and allows for a direct comparison of superradiance emission properties of aggregated molecules to the emission properties of the single molecule. We have found that the fluorescence lifetime of the aggregate is excitation wavelength dependent, and are led to conclude that superradiance by aggregated molecules and energy transfer from monomeric species to the aggregate play important roles in determining the optical dynamics of the aggregated system. We also report some of the photophysical properties of DDPT.