A versatile color tuning strategy for iridium(III) and platinum(II) electrophosphors by shifting the charge-transfer states with an electron-deficient core

By fusing an electron-deficient ring system with the phenyl ring of a 2-phenylpyridine (ppy)-type ligand, a new and synthetically versatile strategy for the phosphorescence color tuning of cyclometalated iridium(III) and platinum(II) metallophosphors has been established. Two robust red electrophosphors with enhanced electron-injection/electron-transporting features were prepared by using an electron-trapping fluoren-9-one chromophore in the ligand design. The thermal, photophysical, redox and electrophosphorescent properties of these complexes are reported. These exciting results can be attributed to a switch of the metal-to-ligand charge-transfer (MLCT) character of the transition from the pyridyl groups in the traditional Ir-III or Pt-II ppy-type complexes to the electron-deficient ring core, and the spectral assignments corroborate well with the electrochemical data as well as the timedependent density functional theory (TD-DFT) calculations. The electron-withdrawing character of the fused ring results in much more stable MLCT states, inducing a substantial red-shift of the triplet emission energy from yellow to red for the Ir-III complex and even green to red for the PtII counterpart.

Synthesis, characterization and fabrication on a glassy carbon electrode of a tetra-iron substituted sandwich-type pentadecatungstodiarsenate heteropolyanion

A novel sandwich-type compound, Na-12[Fe-4(H2O)(2)(As2W15O56)2].41H(2)O, has been synthesized. The compound was well-characterized by means of IR, UV-vis, W-183 NMR and elemental analyses. The compound crystallizes in the triclinic, P (1) over bar symmetry group. The structure of the compound is similar to that of Na-16[M-4(H2O)(2)(As2W15O56)(2)].nH(2)O (M = Cu, Zn, Co, Ni, Mn, Cd), and consists of an oxo-aqua tetranuclear iron core, [(Fe4O14)-O-III(H2O)(2)], sandwiched by two trivacant alpha-Wells-Dawson structural moieties, alpha-[As2W15O56]. Redoxelectrochemistry of the compound has been studied in buffer solutions at pH = 4.7 using polarography and cyclic voltammetry ( CV). The compound exhibited four one-electron couples associated with the Fe(III) center followed by three four-electron redox processes attributed to the tungsten-oxo framework. The compound-containing monolayer and multilayer films have been fabricated on a 4-aminobenzoic acid modified glassy carbon electrode surface by alternating deposition with a quaternized poly(4-vinylpyridine) partially complexed with [Os(bpy)(2)Cl](2+/-). CV, X-ray photoelectron spectroscopy (XPS), UV-vis spectroscopy and atomic force microscopy (AFM) have been used to characterize the multilayer films.

A novel terbium (III) beta-diketonate complex as thin film for optical device application

A novel terbium complex, Tb(acac)(3)AAP (acac: acetylacetone, AAP: 4-amino-antipyrine), was synthesized and its luminescent properties were studied. When it was used as an emitting center, triple-layer-type device with a structure of glass substrate/ITO (indium-tin oxide)/TPD (N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine)./Tb(acac)(3)AAP/PBD (2-(4-biphenyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole) or Alq(3) (tris(8-hydroxyquinolinato) aluminum)/Al (aluminum) exhibited bright characteristic emission of terbium ion upon applying d.c. voltage. The maximum luminance of the device is 56 cd/m(2) at 19 V and the maximum luminance efficiency is 0.357 lm/W.

Bulk modulus of ternary chalcopyrite A(I)B(III)C(2)(VI) and A(II)B(IV)C(2)(V) semiconductors

Based on the complex crystal chemical bond theory, the formula of Liu and Cohen's, which is only suitable for one type of bond, has been extended to calculate the bulk modulus of ternary chalcopyrite A(I)B(III)C(2)(VI) and A(II)B(IV)C(2)(V) which contains two types of bonds. The calculated results are in fair agreement with the previous theoretical values reported and experimental values. (C) 1998 Elsevier Science Ltd. All rights reserved.

Extraction and separation of heavy rare earth (III) with Extraction Resin containing di(2,4,4-trimethyl pentyl) phosphinic acid (Cyanex 272)

Extraction resins, of the type of;levextrel, (which is a collective term for styrene/divinylbenzene based copolymers of predominantly macroporous structure that contain a selective extractant) are important for the recovery and separation of metal ions, as they combine features of solvent extraction and ion exchange resins. This paper presents the results of the adsorption of heavy rare earth ions (Ho(III), Er(III), Tm(III), Yb(III), Lu(III) and Y(III)) from hydrochloric acid solutions at 0.2 mol/L ionic strength and 50 degrees C by the extraction resin containing di (2,4,4-trimethyl pentyl) phosphinic acid (Cyanex 272) and the chromatographic separation of (Er(III), Tm(III) and Yb(III)). Technological separation products, with purity and yield of Tm2O3 >99.97%, >80%, Er2O3 >99.9%, >94% and Yb2O3 >99.8%, >80% respectively, have been obtained from a feed having the composition Tm2O3 60%, Er2O3 10%, and Yb2O3 3%, the others 27%. The distribution coefficients, extraction equilibrium constants and separation factors have been determined as a function of acidity, loading of the resin and rare earths, flow rates and column ratios. The resolutions and efficiencies of separation of Er/Tm/Yb each other have been calculated. The stoichiometry of the extraction of rare earth ions has been suggested as well.

Luminescence properties of the Langmuir-Blodgett film of terbium(III) stearoylanthranilate

Terbium(III) stearoylanthranilate has been prepared as a high property Z-type Langmuir-Blodgett (LB) film on various substrates by a vertical transfer process. The UV-visible absorption spectra and the low angle X-ray diffraction peaks have been collected in order to investigate the molecular arrangement and aggregation in the LB films. The average molecular orientation in multilayer stacking was determined by Attenuated Total Reflection Spectroscopy. The influence of the chemical environment of terbium within the LB films on the luminescence properties has been discussed. (C) 1997 Elsevier Science S.A.

Influence of crystal structure on the luminescence properties of bismuth(III), europium(III) and dysprosium(III) in Y2SiO5

The luminescence properties of Bi3+, EU(3+), Dy3+ and energy transfer from Bi3+ to Dy3+ and EU(3+) have been studied in two modifications of Y2SiO5 (low-temperature X(1) type and high-temperature X(2) type) and discussed in relation to their crystal structures. The Bi3+ ion luminesces in the blue region of the spectrum in X(1)-Y2SiO5 but in the UV region in X(2)-Y2SiO5. Two obviously different luminescent centres have been observed for Bi3+ and Eu3+ ill X(1)-Y2SiO5, but only one has been seen in X(2)-Y2SiO5. The Stokes shift (9200 cm(-1)) for Bi3+ in X(1)-Y2SiO5 is much larger than that (5000 cm(-1)) in X(2)-Y2SiO5. This suggests that the host lattice is more rigid in X(2)-Y2SiO5 than in X(1)-Y2SiO5. As a result, the Bi3+, EU(3+) and Dy3+ ions show higher emission intensity in the former than in the latter type. X(1)-Y2SiO5 is more suitable for Bi3+ --> EU(3+) energy transfer and X(2)-Y2SiO5 is more suitable for Bi3+ --> Dy3+ energy transfer.

A WOUND-TYPE LITHIUM POLYANILINE SECONDARY CELL

A wound-type cell with a polyaniline (PAn) positive electrode, a LiClO4-propylene carbonate (PC) electrolyte, and a lithium foil negative electrode has been constructed. The two electrodes are separated by a polypropylene separator. The PAn is deposited on carbon felt from a HClO4 solution containing aniline by galvanostatic or potentiostatic electrolysis. Using cyclic voltammetry charge/discharge cycles and charge/retention tests, the following results have been obtained: (i) reversibility of the charge/discharge reaction of the PAn electrode is very good; (ii) more than 50 charge/discharge cycles at 80% charge/discharge efficiency and 260 W h kg-1 discharge energy density can be achieved at 50 mA between 2 and 4 V; (iii) the open-circuit voltage and the capacity retention of the battery after storage at open-circuit for 60 days are 3.4 V and 33%, respectively.

Simulation of multigate SOI transistors with silicon, germanium and III-V channels

In this work by employing numerical three-dimensional simulations we study the electrical performance and short channel behavior of several multi-gate transistors based on advanced SOI technology. These include FinFETs, triple-gate and gate-all-around nanowire FETs with different channel material, namely Si, Ge, and III-V compound semiconductors, all most promising candidates for future nanoscale CMOS technologies. Also, a new type of transistor called “junctionless nanowire transistor” is presented and extensive simulations are carried out to study its electrical characteristics and compare with the conventional inversion- and accumulation-mode transistors. We study the influence of device properties such as different channel material and orientation, dimensions, and doping concentration as well as quantum effects on the performance of multi-gate SOI transistors. For the modeled n-channel nanowire devices we found that at very small cross sections the nanowires with silicon channel are more immune to short channel effects. Interestingly, the mobility of the channel material is not as significant in determining the device performance in ultrashort channels as other material properties such as the dielectric constant and the effective mass. Better electrostatic control is achieved in materials with smaller dielectric constant and smaller source-to-drain tunneling currents are observed in channels with higher transport effective mass. This explains our results on Si-based devices. In addition to using the commercial TCAD software (Silvaco and Synopsys TCAD), we have developed a three-dimensional Schrödinger-Poisson solver based on the non-equilibrium Green’s functions formalism and in the framework of effective mass approximation. This allows studying the influence of quantum effects on electrical performance of ultra-scaled devices. We have implemented different mode-space methodologies in our 3D quantum-mechanical simulator and moreover introduced a new method to deal with discontinuities in the device structures which is much faster than the coupled-mode-space approach.

Ligament-derived matrix stimulates a ligamentous phenotype in human adipose-derived stem cells.

Human adipose stem cells (hASCs) can differentiate into a variety of phenotypes. Native extracellular matrix (e.g., demineralized bone matrix or small intestinal submucosa) can influence the growth and differentiation of stem cells. The hypothesis of this study was that a novel ligament-derived matrix (LDM) would enhance expression of a ligamentous phenotype in hASCs compared to collagen gel alone. LDM prepared using phosphate-buffered saline or 0.1% peracetic acid was mixed with collagen gel (COL) and was evaluated for its ability to induce proliferation, differentiation, and extracellular matrix synthesis in hASCs over 28 days in culture at different seeding densities (0, 0.25 x 10(6), 1 x 10(6), or 2 x 10(6) hASC/mL). Biochemical and gene expression data were analyzed using analysis of variance. Fisher's least significant difference test was used to determine differences between treatments following analysis of variance. hASCs in either LDM or COL demonstrated changes in gene expression consistent with ligament development. hASCs cultured with LDM demonstrated more dsDNA content, sulfated-glycosaminoglycan accumulation, and type I and III collagen synthesis, and released more sulfated-glycosaminoglycan and collagen into the medium compared to hASCs in COL (p type by hASCs, and may provide a novel scaffold material for ligament engineering applications.

CaII K interstellar observations towards early-type disc and halo stars - distances to intermediate- and high-velocity clouds

We compare existing high spectral resolution (R = lambda/Deltalambda similar to 40 000) Ca II Kobservations (lambda(air) = 3933.66 Angstrom) towards 88 mainly B-type stars, and new observations taken using the Intermediate dispersion Spectrograph and Imaging System (ISIS) on the William Herschel Telescope at R similar to 10 000 towards three stars taken from the Palomar-Green Survey, with 21-cm HI emission-line profiles, in order to search for optical absorption towards known intermediate- and high-velocity cloud complexes. Given certain assumptions, limits to the gas phase abundance of Ca II are estimated for the cloud components. We use the data to derive the following distances from the Galactic plane (z). (i) Tentative lower z-height limits of 2800 and 4100 pc towards complex C using lack of absorption in the spectra of HD341617 and PG 0855 + 294, respectively. (ii) A weak lower z-height of 1400 pc towards complex WA-WB using lack of absorption in EC 09470-1433 and a weak lower limit of 2470 pc using lack of absorption in EC 09452-1403. (iii) An upper z- height of 2470 pc towards a southern intermediate- velocity cloud (IVC) with v(LSR) = -55 km s(-1) using PG 2351 + 198. (iv) Detection of a possible IVC in Ca II absorption at v(LSR) = +52 km s(-1) using EC 20104-2944. No associated HI in emission is detected. At this position, normal Galactic rotation predicts velocities of up to similar to+ 25 km s(-1). The detection puts an upper z-height of 1860 pc to the cloud. (v) Tentative HI and Ca II K detections towards an IVC at similar to+70 km s(-1) in the direction of high-velocity cloud (HVC) complex WE, sightline EC 06387-8045, indicating that the IVC may be at a z-height lower than 1770 pc. (vi) Detection of Ca II K absorption in the spectrum of PG 0855 + 294 in the direction of IV20, indicating that this IVC has a z-height smaller than 4100 pc. (vii) A weak lower z-height of 4300 pc towards a small HVC with v(LSR) = +115 km s(-1) at l, b = 200degrees, + 52degrees, using lack of absorption in the Ca II K spectrum of PG 0955 + 291.

Boron abundances in B-type stars: A test of rotational depletion during main-sequence evolution

Boron abundances have been derived for seven main-sequence B- type stars from Hubble Space Telescope STIS spectra around the B III lambda2066 line. In two stars, boron appears to be undepleted with respect to the presumed initial abundance. In one star, boron is detectable but is clearly depleted. In the other four stars, boron is undetectable, implying depletions of 1-2 dex. Three of these four stars are nitrogen enriched, but the fourth shows no enrichment of nitrogen. Only rotationally induced mixing predicts that boron depletions are unaccompanied by nitrogen enrichments. The inferred rate of boron depletion from our observations is in good agreement with these predictions. Other boron-depleted nitrogen-normal stars are identified from the literature. In addition, several boron- depleted nitrogen-rich stars are identified, and while all fall on the boron-nitrogen trend predicted by rotationally induced mixing, a majority have nitrogen enrichments that are not uniquely explained by rotation. The spectra have also been used to determine iron group (Cr, Mn, Fe, and Ni) abundances. The seven B-type stars have near-solar iron group abundances, as expected for young stars in the solar neighborhood. We have also analyzed the halo B-type star PG 0832 + 676. We find [Fe/H] = -0.88 +/- 0.10, and the absence of the B III line gives the upper limit [B/H] <-2.5. These and other published abundances are used to infer the star's evolutionary status as a post-asymptotic giant branch star.

A Novel Multilocus Sequence Typing Scheme for the Opportunistic Pathogen Propionibacterium acnes and Characterisation of Type I Cell Surface-Associated Antigens.

We have developed a novel Multilocus Sequence Typing Scheme (MLST) and database (http://pubmlst.org/pacnes/) for Propionibacterium acnes based on the analysis of seven core housekeeping genes. The scheme, which was validated against previously described antibody, single locus and Random Amplification of Polymorphic DNA (RAPD) typing methods, displayed excellent resolution and differentiated 123 isolates into 37 sequence types (ST). An overall clonal population structure was detected with six eBURST groups representing the major clades I, II and III, along with two singletons. Two highly successful and global clonal lineages, ST6 (type IA) and ST10 (type IB1), representing 65% of this current MLST isolate collection were identified. The ST6 clone and closely related single locus variants (SLV), which comprise a large clonal complex CC6, dominated isolates from patients with acne, and were also significantly associated with ophthalmic infections. Our data therefore supports an association between acne and P. acnes strains from the type IA cluster and highlights the role of a widely disseminated clonal genotype in this condition. Characterisation of type I cell surface-associated antigens that are not detected in ST10 or strains of type II and III identified two dermatan-sulphate-binding proteins with putative phase/antigenic variation signatures. We propose that the expression of these proteins by type IA organisms contributes to their role in the pathophysiology of acne and helps explain the recurrent nature of the disease. The MLST scheme and database described in this study should provide a valuable platform for future epidemiological and evolutionary studies of P. acnes.

Cell-collagen interactions: the use of peptide Toolkits to investigate collagen-receptor interactions

Fibrillar collagens provide the most fundamental platform in the vertebrate organism for the attachment of cells and matrix molecules. we have identified specific sites in collagens to which cells can attach, either directly or through protein intermediaries. Using Toolkits of triple-helical peptides, each peptide comprising 27 residues of collagen primary sequence and overlapping with its neighbours by nine amino acids, we have mapped the binding of receptors and other proteins on to collagens II or III. Integrin alpha 2 beta 1 binds to several GXX'GER motifs within the collagens, the affinities of which differ sufficiently to control cell adhesion and migration independently of the cellular regulation of the integrin. The platelet receptor, Gp (glycoprotein) VI binds well to GPO (where 0 is hydroxyproline)-containing model peptides, but to very few Toolkit peptides, suggesting that sequence in addition to GPO triplets is important in defining GpVI binding. The Toolkits have been applied to the plasma protein vWF (von Willebrand factor), which binds to only a single sequence, identified by truncation and amino acid substitution within Toolkit peptides, as GXRGQOGVMGFO in collagens II and III. Intriguingly, the receptor tyrosine kinase, DDR2 (discoidin domain receptor 2) recognizes three sites in collagen II, including its vWF-binding site, although the amino acids that support the interaction differ slightly within this motif. Furthermore, the secreted protein BM-40 (basement membrane protein 40) also binds well to this same region. Thus the availability of extracellular collagen-binding proteins may be important in regulating and facilitating direct collagen-receptor interaction.

Glycoprotein VI/Fc receptor gamma chain-independent tyrosine phosphorylation and activation of murine platelets by collagen

We have investigated the ability of collagen to induce signalling and functional responses in suspensions of murine platelets deficient in the FcRgamma (Fc receptor gamma) chain, which lack the collagen receptor GPVI (glycoprotein VI). In the absence of the FcRgamma chain, collagen induced a unique pattern of tyrosine phosphorylation which was potentiated by the thromboxane analogue U46619. Immunoprecipitation studies indicated that neither collagen alone nor the combination of collagen plus U46619 induced phosphorylation of the GPVI-regulated proteins Syk and SLP76 (Src homology 2-containing leucocyte protein of 76 kDa). A low level of tyrosine phosphorylation of phospholipase Cgamma2 was observed, which was increased in the presence of U46619, although the degree of phosphorylation remained well below that observed in wild-type platelets (similar to 10%). By contrast, collagen-induced phosphorylation of the adapter ADAP (adhesion- and degranulation-promoting adapter protein) was substantially potentiated by U46619 to levels equivalent to those observed in wild-type platelets. Collagen plus U46619 also induced significant phosphorylation of FAK (focal adhesion kinase). The functional significance of collagen-induced non-GPVI signals was highlighted by the ability of U46619 and collagen to induce the secretion of ATP in FcRgamma chain-deficient platelets, even though neither agonist was effective alone. Protein tyrosine phosphorylation and the release of ATP were abolished by the anti(alpha2 integrin) antibodies Ha1/29 and HMalpha2, but not by blockade of alphaIIbbeta3. These results illustrate a novel mechanism of platelet activation by collagen which is independent of the GPVI-FcRgamma chain complex, and is facilitated by binding of collagen to integrin alpha2beta1.