A multifunctional iridium carbazolyl orange phosphor for high performance two-element WOLED exploiting exciton-managed fluorescence/phosphorescence

By attaching a bulky, inductively electron-with drawing trifluoromethyl (CF3) group on the pyridyl ring of the rigid 2-[3(N-phenylcarbazolyl)]pyridine cyclometalated ligand, we successfully synthesized a new heteroleptic orange-emitting phosphorescent iridium(III) complex [Ir(L-1)(2)(acac)] 1 (HL1=5-trifluoromethyl-2-[3-(N-phenylcarbazolyl)]pyridine, Hacac = acetylacetone) in good yield.

Manipulating charge-transfer character with electron-withdrawing main-group moieties for the color tuning of iridium electrophosphors

A new and synthetically versatile strategy has been developed for the phosphorescence color tuning of cyclometalated iridium phosphors by simple tailoring of the phenyl ring of ppy (Hppy=2-phenylpyridine) with various main-group moieties in [Ir(ppy-X)(2)(acac)] (X=B(Mes)(2), SiPh3, GePh3, NPh2, POPh2, OPh, SPh, SO2Ph). This can be achieved by shifting the charge-transfer character from the pyridyl groups in some traditional iridium ppy-type complexes to the electron-withdrawing main-group moieties and these assignments were supported by theoretical calculations.

Robust Tris-Cyclometalated Iridium(III) Phosphors with Ligands for Effective Charge Carrier Injection/Transport: Synthesis, Redox, Photophysical, and Electrophosphorescent Behavior

With the target to design and develop new functionalized green triplet light emitters that possess distinctive electronic properties for robust and highly efficient phosphorescent organic light-emitting diodes (PHOLEDs), a series of bluish-green to yellow-green phosphorescent tris-cyclometalated homoleptic iridium(III) complexes [Ir(ppy-X)(3)] (X=SiPh3, GePh3, NPh2, POPh2, OPh, SPh, SO2Ph, Hppy=2-phenylpyridine) have been synthesized and fully characterized by spectroscopic, redox, and photophysical methods

The Reasons for Ligand-Dependent Quantum Yields and Absorption Spectrum of Four Polypyridylruthenium(II) Complexes with a Tetrazolate-Based Ligand: TDDFT Study

The quantum yield, lifetime, and absorption spectrum of four [Ru(bpy)(2)L](+) [where bpy is 2,2'-bipyridyl; L is represented by the deprotonated form of 2-(1H-tetrazol-5-yl)pyridine (L1) or 2-(1H-tetrazol-5-yl)pyrazine (L2)], as well as their methylated complexes [Ru(bpy)(2)LMe](2+) (RuL1Me and RuL2Me) are closely ligand dependent. In this paper, density functional theory (DFT) and time-dependent DFT (TDDFT) were performed to compare the above properties among these complexes. The calculated results reveal that the replacement of pyridine by pyrazine or the attachment of a CH3 group to the tetrazolate ring greatly increases the pi-accepting ability of the ancillary ligands.

Electronic structures and chemical bonding in transition metal monosilicides MSi (M=3d, 4d, 5d elements)

Bond distances, vibrational frequencies, electron affinities, ionization potentials, dissociation energies, and dipole moments of the title molecules in neutral, positively, and negatively charged ions were studied using the density functional method. Ground state was assigned for each species. The bonding patterns were analyzed and compared with both the available data and across the series. It was found that besides an ionic component, covalent bonds are formed between the metal s, d orbitals and the silicon 3p orbital. The covalent character increases from ScSi (YSi) to NiSi (PdSi) for 3d (4d) metal monosilicides, then decreases. For 5d metal monosilicides, the covalent character increases from LaSi to OsSi, then decreases. For the dissociation of cations, the dissociation channel depends on the magnitude of the ionization potential between metal and silicon. If the ionization potential of the metal is smaller than that of silicon, channel MSi+-> M++Si is favored. Otherwise, MSi+-> M+Si+ will be favored. A similar behavior was observed for anions, in which the dissociation channel depends on the magnitude of electron affinity.

Geometries and electronic properties of AunPdm (n=1-4, m =-1, 0, 1) clusters

Possible conformers for AunPdm (n = 1-4, m = -1, 0, 1) clusters have been presented and studied by use of density functional theory. The results indicate that for n = 2, linear conformer with C-infinityv symmetry is the most stable for anion species, while for cation and neutral species, conformer with C-2v symmetry is the most stable. For n = 3, 4, conformers with C-2v symmetry (kite-shape) are energetically favored. The calculated electron affinities (EAs) and vertical detachment energies (VDEs) are in good agreement with experiments for n = 1-4. It is also interesting to note that for even n (n = 2, 4), the most stable conformers do not give the best agreement between calculated and experimental EA and VDE values, while for odd n (n = 3), the lowest energy conformer also gives the best agreement. The ionization potentials (IPs) of AunPd clusters are calculated as well.

X-ray crystal structure and molecular mechanics calculations of (2,6-iso-dipropyl-phenylamide) dimethyl (tetra-methylcyclopenta-dienyl) silane titanium dichloride

Crystal and molecular structure of (2.6-dipropylphenylamide) dimethyl (tetra-methyl cyclopentadienyl) silane titanium dichloride (I) was fully characterized by X-ray diffraction. The crystal is obtained from a mixture of ether/hexane as orthorhombic. with a = 12.658 (3) Angstrom. b = 16.62 (3) Angstrom. c = 11.760 (2) Angstrom. V = 2474.2 (9) Angstrom(3). Z = 4, space group Pnma. R = 0.0399; Componud I compose of the pi-bounded ring with its dimethylsilyl-dipropyl phenyl amido group and the two terminal chloride atoms coordinated to central metal to form a so-called constrained geometry catalyst (CGC) structure. The result of molecular mechanics (MM) calculations on compound I shows that bond lengths and bond angles from the MM calculation are comparable to the data obtained from the X-ray diffraction study. The relation of the structure of CGCs and their catalytic activity by MM calculations is also discussed.

Elasticity, stability, and ideal strength of beta-SiC in plane-wave-based ab initio calculations

On the basis of the pseudopotential plane-wave method and the local-density-functional theory, this paper studies energetics, stress-strain relation, stability, and ideal strength of beta-SiC under various loading modes, where uniform uniaxial extension and tension and biaxial proportional extension are considered along directions [001] and [111]. The lattice constant, elastic constants, and moduli of equilibrium state are calculated and the results agree well with the experimental data. As the four SI-C bonds along directions [111], [(1) over bar 11], [11(1) over bar] and [111] are not the same under the loading along [111], internal relaxation and the corresponding internal displacements must be considered. We find that, at the beginning of loading, the effect of internal displacement through the shuffle and glide plane diminishes the difference among the four Si-C bonds lengths, but will increase the difference at the subsequent loading, which will result in a crack nucleated on the {111} shuffle plane and a subsequently cleavage fracture. Thus the corresponding theoretical strength is 50.8 GPa, which agrees well with the recent experiment value, 53.4 GPa. However, with the loading along [001], internal relaxation is not important for tetragonal symmetry. Elastic constants during the uniaxial tension along [001] are calculated. Based on the stability analysis with stiffness coefficients, we find that the spinodal and Born instabilities are triggered almost at the same strain, which agrees with the previous molecular-dynamics simulation. During biaxial proportional extension, stress and strength vary proportionally with the biaxial loading ratio at the same longitudinal strain.

Forced extension of P-selectin construct using steered molecular dynamics

P-selectin, a 70-nm-long cellular adhesive molecule, possesses elastic and extensible properties when neutrophils roll over the activated endotheliam of blood vessel in inflammatory reaction. Transient formation and dissociation of P-selectin/ligand bond on applied force of blood flow induces the extension of P-selectin and relevant ligands. Steered molecular dynamics simulations were performed to stretch a single P-selectin construct consisting of a lectin (Lec) domain and an epithelial growth factor (EGF)-like domain, where P-selectin construct was forced to extend in water with pulling velocities of 0.005-0.05 nm/ps and with constant forces of 1000-2500 pN respectively. Resulting force-extension profiles exhibited a dual-peak pattern on various velocities, while both plateaus and shoulders appeared in the extension-time profiles on various forces. The force or extension profiles along stretching pathways were correlated to the conformational changes, suggesting that the structural collapses of P-selectin Lec/EGF domains were mainly attributed to the burst of hydrogen bonds within the major beta sheet of EGF domain and the disruptions of two hydrophobic cores of Lee domain. This work furthers the understanding of forced dissociation of P-selectin/ligand bond.

Studies of magnetic interactions in Ni-doped ZnO from first-principles calculations

The magnetic interactions in Ni-doped ZnO are calculated using GGA and GGA + U method of density functional theory. The following three cases: (i) Ni-doped ZnO, (ii) (Ni, Al)-codoped ZnO, and (iii) (Ni, Li)-codoped ZnO are studied. The ferromagnetic ordering is always favorable for the three cases within GGA method. However, the ferromagnetic state is sometimes favorable after treating within the method of GGA + U. The GGA underestimates the correlated interactions especially when the Ni ions align directly to each other. (C) 2007 Elsevier B.V. All rights reserved.

Characterize dynamic conformational space of human CCR5 extracellular domain by molecular modeling and molecular dynamics simulation

The chemokine receptor CCR5 is the receptor for several chemokines and major coreceptor for R5 human immunodeficiency virus type-1 strains entry into cell. Three-dimensional models of CCR5 were built by using homology modeling approach and 1 ns molecular dynamics (MD) simulation, because studies of site-directed mutagenesis and chimeric receptors have indicated that the N-terminus (Nt) and extracellular loops (ECLs) of CCR5 are important for ligands binding and viral fusion and entry, special attention was focused on disulfide bond function, conformational flexibility, hydrogen bonding, electrostatic interactions, and solvent-accessible surface area of Nt and ECLs of this protein part. We found that the extracellular segments of CCR5 formed a well-packet globular domain with complex interactions occurred between them in a majority of time of MID simulation, but Nt region could protrude from this domain sometimes. The disulfide bond Cys20-Cys269 is essential in controlling specific orientation of Nt region and maintaining conformational integrity of extracellular domain. RMS comparison analysis between conformers revealed the ECL1 of CCR5 stays relative rigid, whereas the ECL2 and Nt are rather flexible. Solvent-accessible surface area calculations indicated that the charged residues within Nt and ECL2 are often exposed to solvent. Integrating these results with available experimental data, a two-step gp120-CCR5 binding mechanism was proposed. The dynamic interaction of CCR5 extracellular domain with gp120 was emphasized. (C) 2004 Elsevier B.V. All rights reserved.

Molecular phylogeny of the specialized schizothoracine fishes (Teleostei : Cyprinidae), with their implications for the uplift of the Qinghai-Tibetan Plateau

Molecular phylogeny of three genera containing nine species and subspecies of the specialized schizothoracine fishes are investigated based on the complete nucleotide sequence of mitochondrial cytochrome b gene. Meantime relationships between the main cladogenetic events of the specialized schizothoracine fishes and the stepwise uplift of the Qinghai-Tibetan Plateau are also conducted using the molecular clock, which is calibrated by geological isolated events between the upper reaches of the Yellow River and the Qinghai Lake. Results indicated that the specialized schizothoracine fishes are not a monophyly. Five species and subspecies of Ptychobarbus form a monophyly. But three species of Gymnodiptychus do not form a monophyly. Gd. integrigymnatus is a sister taxon of the highly specialized schizothoracine fishes while Gd. pachycheilus has a close relation with Gd. dybowskii, and both of them are as a sister group of Diptychus maculatus. The specialized schizothoracines fishes might have originated during the Miocene (about 10 MaBP), and then the divergence of three genera happened during late Miocene (about 8 MaBP). Their main specialization occurred during the late Pliocene and Pleistocene (3.54-0.42 MaBP). The main cladogenetic events of the specialized schizothoracine fishes are mostly correlated with the geological tectonic events and intensive climate shift happened at 8, 3.6, 2.5 and 1.7 MaBP of the late Cenozoic. Molecular clock data do not support the hypothesis that the Qinghai-Tibetan Plateau uplifted to near present or even higher elevations during the Oligocene or Miocene, and neither in agreement with the view that the plateau uplifting reached only to an altitude of 2000 in during the late Pliocene (about 2.6 MaBP).

Molecular evolution of connective tissue growth factor in Cyprinidae (Teleostei : Cypriniformes)

Connective tissue growth factor (CTGF) plays an important role in regulation of cell growth, differentiation, apoptosis and individual development in animals. The study of sequences variation and molecular evolution of CTGF gene across various species of the cyprinid could be helpful for understanding of speciation and gene divergence in this kind of fish. In this study, 19 novel sequences of CTGF gene were obtained from the representative species of the family Cyprinidae using PCR amplification, cloning and sequencing. Phylogenetic relationships of Cyprinidae were reconstructed by neighbor-joining (NJ), maximum parsimony (MP), maximum likelihood (ML) and Bayesian method. Oryzias latipes from the family Cyprinodontidae was assigned to be the outgroup taxon. Leuciscini and Barbini were clustered into the monophyletic lineages, respectively, with the high nodal supports. The estimation of the ratio of non-synonymous to synonymous substitution (dN/dS) for the various branches indicated that there stood the different evolution rates between the Leuciscini and the Barbini. With the ratio of dN/dS of the Leuciscini being lower than that of the Barbini, species within the Barbini were demonstrated to be subjected to the relatively less selection pressure and under the relaxable evolution background. A 6 by indel (insertion/deletion) was found at the 5' end of CTGF gene of Cyprinidae, and this 6 by deletion only appeared in the Leuciscini, which is a typical characteristic of the Leuciscini and provides evidence for the monophylogeny of the Leuciscini. For the amino acid sequences of CTGF protein, the most variations and indels were distributed in the signal region and IGFBP region of this protein, implying that these variations were correlated with the regulation of the CTGF gene expression and protein activity. (c) 2007 National Natural Science Foundation of China and Chinese Academy of Sciences. Published by Elsevier Limited and Science in China Press. All rights reserved.

Molecular phylogeny of the specialized schizothoracine fishes (Teleostei : Cyprinidae), with their implications for the uplift of the Qinghai-Tibetan Plateau

Molecular phylogeny of three genera containing nine species and subspecies of the specialized schizothoracine fishes are investigated based on the complete nucleotide sequence of mitochondrial cytochrome b gene. Meantime relationships between the main cladogenetic events of the specialized schizothoracine fishes and the stepwise uplift of the Qinghai-Tibetan Plateau are also conducted using the molecular clock, which is calibrated by geological isolated events between the upper reaches of the Yellow River and the Qinghai Lake. Results indicated that the specialized schizothoracine fishes are not a monophyly. Five species and subspecies of Ptychobarbus form a monophyly. But three species of Gymnodiptychus do not form a monophyly. Gd. integrigymnatus is a sister taxon of the highly specialized schizothoracine fishes while Gd. pachycheilus has a close relation with Gd. dybowskii, and both of them are as a sister group of Diptychus maculatus. The specialized schizothoracines fishes might have originated during the Miocene (about 10 MaBP), and then the divergence of three genera happened during late Miocene (about 8 MaBP). Their main specialization occurred during the late Pliocene and Pleistocene (3.54-0.42 MaBP). The main cladogenetic events of the specialized schizothoracine fishes are mostly correlated with the geological tectonic events and intensive climate shift happened at 8, 3.6, 2.5 and 1.7 MaBP of the late Cenozoic. Molecular clock data do not support the hypothesis that the Qinghai-Tibetan Plateau uplifted to near present or even higher elevations during the Oligocene or Miocene, and neither in agreement with the view that the plateau uplifting reached only to an altitude of 2000 in during the late Pliocene (about 2.6 MaBP).

Defects in gallium nitride nanowires: First principles calculations

Atomic configurations and formation energies of native defects in an unsaturated GaN nanowire grown along the [001] direction and with (100) lateral facets are studied using large-scale ab initio calculation. Cation and anion vacancies, antisites, and interstitials in the neutral charge state are all considered. The configurations of these defects in the core region and outermost surface region of the nanowire are different. The atomic configurations of the defects in the core region are same as those in the bulk GaN, and the formation energy is large. The defects at the surface show different atomic configurations with low formation energy. Starting from a Ga vacancy at the edge of the side plane of the nanowire, a N-N split interstitial is formed after relaxation. As a N site is replaced by a Ga atom in the suboutermost layer, the Ga atom will be expelled out of the outermost layers and leaves a vacancy at the original N site. The Ga interstitial at the outmost surface will diffuse out by interstitialcy mechanism. For all the tested cases N-N split interstitials are easily formed with low formation energy in the nanowires, indicating N-2 molecular will appear in the GaN nanowire, which agrees well with experimental findings.