Life of flame particles embedded in premixed flames interacting with near isotropic turbulence

Flame particles are surface points that always remain embedded on, by comoving with a given iso-scalar surface within a flame. Tracking flame particles allow us to study the fate of propagating surface locations uniquely identified throughout their evolution with time. In this work, using Direct Numerical Simulations we study the finite lifetime of such flame particles residing on iso-temperature surfaces of statistically planar H-2-air flames interacting with near-isotropic turbulence. We find that individual flame particles as well as their ensemble, experience progressively increasing tangential straining rate (K-t) and increasing negative curvature (kappa) near the end of their lifetime to finally get annihilated. By studying two different turbulent flow conditions, flame particle tracking shows that such tendency of local flame surfaces to be strained and cusped towards pinch-off from the main surface is a rather generic feature, independent of initial conditions, locations and ambient turbulence intensity levels. The evolution of the alignments between the flame surface normals and the principal components of the local straining rates are also tracked. We find that the surface normals initially aligned with the most extensive principal strain rate components, rotate near the end of flame particles' lifetime to enable preferential alignment between the surface tangent and the most extensive principal strain rate component. This could explain the persistently increasing tangential strain rate, sharp negative curvature formation and eventual detachment. (C) 2014 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Synthesis of Eu3+-activated BiOF and BiOBr phosphors: photoluminescence, Judd-Ofelt analysis and photocatalytic properties

A series of Bi1-xEuxOX (X = F and Br; x = 0, 0.01, 0.03 and 0.05) phosphors were synthesized at relatively low temperature and short duration (500 degrees C, 1 h). Rietveld refinement results verified that all the compounds were crystallized in the tetragonal structure with space group P4/nmm (no. 129). Photoluminescence spectra exhibit characteristic luminescence D-5(0) -> F-7(J) (J = 0-4) intra-4f shell Eu3+ ion transitions. The magnetic dipole (D-5(0) -> F-7(1)) transition dominates the emission of BiOF:Eu3+, while the electric dipole (D-5(0) -> F-7(2)) peak was stronger in BiOBr:Eu3+ phosphors. The evaluated CIE color coordinates for Bi0.95Eu0.05OBr (0.632, 0.358) are close to the commercial Y2O3:Eu3+ (0.645, 0.347) and Y2O2S:Eu3+ (0.647, 0.343) red phosphors. Intensity parameters (Omega(2), Omega(4)) and various radiative properties such as transition rates (A), branching ratios (beta), stimulated emission cross-section (sigma(e)), gain bandwidth (sigma(e) x Delta lambda(eff)) and optical gain (sigma(e) x tau) were calculated using the Judd-Ofelt theory. It was observed that BiOBr:Eu3+ phosphors have a long lifetime (tau) and better optical gain (sigma(e) x tau) as compared to reported Eu3+ doped materials. Furthermore, these compounds exhibit excellent photocatalytic activity for the degradation of rhodamine B dye under visible light irradiation. The determined radiative properties and photocatalytic results revealed that BiOBr:Eu3+ phosphors have potential applications in energy and environmental remedies, such as to develop red phosphors for white light-emitting diodes, red lasers and to remove toxic organic industrial effluents.

Composition dependent non-ideality in aqueous binary mixtures as a signature of avoided spinodal decomposition

We explore the potential energy landscape of structure breaking binary mixtures (SBBM) where two constituents dislike each other, yet remain macroscopically homogeneous at intermediate to high temperatures. Interestingly, we find that the origin of strong composition dependent non-ideal behaviour lies in its phase separated inherent structure. The inherent structure (IS) of SBBM exhibits bi-continuous phase as is usually formed during spinodal decomposition. We draw analogy of this correlation between non-ideality and phase separation in IS to explain observation of non-ideality in real aqueous mixtures of small amphiphilic solutes, containing both hydrophilic and hydrophobic groups. Although we have not been able to obtain IS of these liquids, we find that even at room temperature these liquids sustain formation of fluctuating, transient bi-continuous phase, with limited lifetime (tau less than or similar to 20 ps). While in the model (A, B) binary mixture, the non-ideal composition dependence can be considered as a fluctuation from a phase separated state, a similar scenario is expected to be responsible for the unusually strong non-ideality in these aqueous binary mixtures.

Tailoring local density of optical states to control emission intensity and anisotropy of quantum dots in hybrid photonic-plasmonic templates

We report results of controlled tuning of the local density of states (LDOS) in versatile, flexible, and hierarchical self assembled plasmonic templates. Using 5 nm diameter gold (Au) spherical nanoantenna within a polymer template randomly dispersed with quantum dots, we show how the photoluminescence intensity and lifetime anisotropy of these dots can be significantly enhanced through LDOS tuning. Finite difference time domain simulations corroborate the experimental observations and extend the regime of enhancement to a wider range of geometric and spectral parameters bringing out the versatility of these functional plasmonic templates. It is also demonstrated how the templates act as plasmonic resonators for effectively engineer giant enhancement of the scattering efficiency of these nano antenna embedded in the templates. Our work provides an alternative method to achieve spontaneous emission intensity and anisotropy enhancement with true nanoscale plasmon resonators. (C) 2015 AIP Publishing LLC.

Synthesis and characterization of monometallic rhenium(I) complexes and their application as selective sensors for copper(II) ions

Novel imine functionalized monometallic rhenium(I) polypyridine complexes (1-4) comprising two phenol moieties attached to 2,20-bipyridine ligands L1-L4 have been synthesized and characterized. These complexes exhibit selective and sensitive detection towards copper(II) ions and this is observed through changes in UV-visible absorption, luminescence and time-resolved spectroscopic techniques. An enormous enhancement is observed in emission intensity, quantum yield and luminescence lifetime with the addition of copper(II) ions, and this can be attributed to the restriction of C=N isomerization in the Re(I) complexes. The strong binding between copper(II) ions and these complexes reveals that the binding constant values are in the range of 1.1 x 10(3)-6.0 x 103 M-1. The absorption spectral behavior of the complexes is supported by DFT calculations.

Synthesis of Eu3+-activated BaMoO4 phosphors and their Judd-Ofelt analysis: Applications in lasers and white LEDs

Eu3+-activated BaMoO4 phosphors were synthesized by the nitrate citrate gel combustion method. The Rietveld refinement analysis confirmed that all the compounds were crystallized in the scheelite-type tetragonal structure with I4(1)/a (No. 88) space group. Photoluminescence (PL) spectra of BaMoO4 phosphor reveals broad emission peaks at 465 and 605 nm, whereas the Eu3+-activated BaMoO4 phosphors show intense 615 nm (D-5(0) -> F-7(2)) emission peak. Judd-Ofelt theory was applied to evaluate the intensity parameters (Omega(2), Omega(4)) of Eu3+-activated BaMoO4 phosphors. The transition probabilities (A(T)), radiative lifetime (tau(rad)), branching ratio (beta), stimulated emission cross-section (sigma(e)), gain bandwidth (sigma(e) x Delta lambda(eff)) and optical gain (sigma(e) x tau(rad)) were investigated by using the intensity parameters. CIE color coordinates confirmed that the BaMoO4 and Eu3+-activated BaMoO4 phosphors exhibit white and red luminescence, respectively. The obtained results revealed that the present phosphors can be a potential candidate for red lasers and white LEDs applications. (C) 2015 Elsevier B.V. All rights reserved.

Comparative study of Eu3+ -activated LnOCl (Ln=La and Gd) phosphors and their Judd-Ofelt analysis

Eu3+-activated layered LnOCl (Ln=La and Gd) phosphors were synthesized by the conventional solid-state method at relatively low temperature (700 degrees C) and shorter duration of 2 h. The structural parameters were refined by the Rietveld refinement analysis and confirmed by the high resolution transmission electron microscopy (HRTEM). Both the compounds were crystallized in the tetragonal structure with space group P4/nmm (No. 129). The homogeneity of the elements were analyzed by TEM mapping and found to be uniformly distributed. The photoluminescence spectra revealed that the intensity of D-5(0)-> F-7(2) transition (619 nm) was more intense in Eu3+-activated GdOCl compared to LaOCl. This was due to the property of Gd3+ ions to act as an intermediate sublattice to facilitate the energy transfer to Eu3+ ions. Intensity parameters and radiative properties such as transition probabilities, radiative lifetime and branching ratio were calculated using the Judd-Ofelt theory. The CIE color coordinates result revealed that the Eu3+-activated GdOCl (0.641, 0.354) phosphor was close to the commercial red phosphors like, Y2O3:Eu3+ (0.645, 0.347), (Y2OS)-S-2:Eu3+ (0.647, 0.343) and National Television System Committee (NTSC) (0.67, 0.33). The results suggest that the present GdOCl:Eu3+ compound acts as a potential candidate for red phosphor materials.

Direct Observation of Thermal Equilibrium of Excited Triplet States of 9,10-Phenanthrenequinone. A Time-Resolved Resonance Raman Study

The photochemistry of aromatic ketones plays a key role in various physicochemical and biological processes, and solvent polarity can be used to tune their triplet state properties. Therefore, a comprehensive analysis of the conformational structure and the solvent polarity induced energy level reordering of the two lowest triplet states of 9,10-phenanthrenequinone (PQ) was carried out using nanosecond-time-resolved absorption (ns-TRA), time-resolved resonance Raman (TR3) spectroscopy, and time dependent-density functional theory (TD-DFT) studies. The ns-TRA of PQ in acetonitrile displays two bands in the visible range, and these two bands decay with similar lifetime at least at longer time scales (mu s). Interestingly, TR3 spectra of these two bands indicate that the kinetics are different at shorter time scales (ns), while at longer time scales they followed the kinetics of ns-TRA spectra. Therefore, we report a real-time observation of the thermal equilibrium between the two lowest triplet excited states of PQ assigned to n pi* and pi pi* of which the pi pi* triplet state is formed first through intersystem crossing. Despite the fact that these two states are energetically close and have a similar conformational structure supported by TD-DFT studies, the slow internal conversion (similar to 2 ns) between the T-2(1(3)n pi*) and T-1(1(3)pi pi*) triplet states indicates a barrier. Insights from the singlet excited states of PQ in protic solvents J. Chem. Phys. 2015, 142, 24305] suggest that the lowest n pi* and pi pi* triplet states should undergo hydrogen bond weakening and strengthening, respectively, relative to the ground state, and these mechanisms are substantiated by TD-DFT calculations. We also hypothesize that the different hydrogen bonding mechanisms exhibited by the two lowest singlet and triplet excited states of PQ could influence its ISC mechanism.

Spectral characterizations and photophysical properties of one-step synthesized blue fluorescent 4 `-aryl substituted 2,2 `:6 `,2 `'-terpyridine for OLEDs application

We have synthesized a series of 4'-aryl substituted 2,2':6',2 `'-terpyridine (terpy) derivatives, namely 4'-(4-methylphenyl)-2,2':6',2 `'-terpyridine (C-1), 4'-(2-furyl)-2,2':6'2 `'-terpyridine (C-2), and 4'-(3,4,5-trimethoxyphenyl)-2,2':6',2 `'-terpyridine (C-3). The synthesized terpy compounds were characterized by elemental analyses, FTIR, NMR (H-1 and C-13), and ESI-Mass spectrometry. Photophysical, electrochemical and thermal properties of terpy compounds were systematically studied. Maximum excitation band was observed between 240 and 330 nm using UV-visible spectra, and maximum emission peaks from PL spectra were observed at 385, 405 and 440 nm for C-1, C-2 and C-3 respectively. Fluorescence lifetime (tau) of the fluorophores was found to be 035 and 1.55 ns at the excitation wavelength of 406 nm for C-1 and C-2 respectively, and tau value for C-3 was found to be 0.29 ns at the excitation wavelength of 468 nm. We noticed that the calculated values of HOMO energy levels were increased from 5.96 (C-1) to 6.08 (C-3) eV, which confirms that C-3 derivative is more electrons donating in nature. The calculated electrochemical band gaps were 2.95, 2.82 and 3.02 eV for C-1, C-2 and C-3 respectively. These blue fluorescent emitter derivatives can be used as an electron transport and electroluminescent material to design the blue fluorescent organic light emitting diode (OLED) applications. (C) 2015 Elsevier B.V: All rights reserved.

Strain-Induced Hierarchy of Energy Levels in CdS/ZnS Nanocrystals

Aside of size and shape, the strain induced by the mismatch of lattice parameters between core and shell in the nanocrystalline regime is an additional degree of freedom to engineer the electron energy levels. Herein, CdS/ZnS core/shell nanocrystals (NCs) with shell thickness up to four monolayers are studied. As a manifestation of strain, the low temperature radiative lifetime measurements indicate a reduction in Stokes shift from 36 meV for CdS to 5 meV for CdS/ZnS with four monolayers of overcoating. Concomitant crossover of S- and P-symmetric hole levels is observed which can be understood in the framework of theoretical calculations predicting flipping the hierarchy of ground hole state by the strain in CdS NCs. Furthermore, a nonmonotonic variation of higher energy levels in strained CdS NCs is discussed.

Photocytotoxic luminescent lanthanide complexes of DTPA-bisamide using quinoline as photosensitizer

Lanthanide complexes Ln(DTPAAQ)(DMF)] (1-3) (Ln - Pr (1), Eu (2), Tb (3), H(3)DTPAAQ - N, N `'-bis(3-amidoquinolyl) diethylenetriamine-N, N', N `'-triacetic acid, DMF - N, N-dimethylformamide) were studied for their structures, photophysical properties, DNA and protein binding, DNA photocleavage, photocytotoxicity and cellular internalization. The crystal structures of complexes Ln(DTPAAQ)(DMF)] (1-3) display a discrete mononuclear nine-coordinate {LnN(3)O(6)} tricapped-trigonal prism (TTP) coordination geometry. The europium and terbium complexes show strong luminescence properties in the visible region having a long luminescence lifetime (tau = 0.51-0.64 ms). The conjugated 3-aminoquinoline moieties act as efficient light harvesting antennae, which upon photoexcitation transfer their energy to Eu(III) or Tb(III) for their characteristic D-5(0) -> F-7(J) or D-5(4) -> F-7(J) f-f transitions respectively. The complexes display efficient binding affinity to DNA (K-b = 3.4 x 10(4) - 9.8 x 10(4) M-1) and BSA (KBSA = 3.03 x 10(4) - 6.57 x 10(4) M-1). Europium and terbium complexes give enhanced luminescence upon interacting with CT-DNA suggesting possible luminescence-based sensing applications for these complexes. Complexes 1-3 show moderate cleavage of supercoiled (SC) DNA to its nicked circular (NC) form on exposure to UV-A light of 312 nm involving formation of singlet oxygen (O-1(2)) and hydroxyl radicals (cOH) in type-II and photoredox pathways. Eu(III) and Tb(III) complexes exhibit remarkable photocytotoxicity with human cervical cancer cell line (HeLa) (IC50 = 20.7-28.5 mM) while remaining essentially noncytotoxic up to 150 mM in the dark. Complexes are nontoxic in nature thus suitable for designing cellular imaging agents. Fluorescence microscopy data reveal primarily cytosolic localization of the Eu(III) and Tb(III) complexes in HeLa cells.