Ln(Ln=Y/Gd)VO4:Er3+/Nd3+的制备及发光性能

采用高温固相法制备了Ln（Ln=Y／Gd）VO4掺Er^3＋或Nd^3＋的近红外发光材料。通过X射线粉末衍射（XRD）和光致发光（PL）对样品进行了表征。结果表明：所得产品结晶良好，属于四方晶系，锆石结构。研究了Er^3＋，Nd^3＋的含量、煅烧时间、煅烧温度等对材料近红外发光性质的影响。在Ln（Ln=Y／Gd）VO4：Er^3＋／Nd^3＋中，存在明显的从VO4^3-向Er^3＋／Nd^3＋的能量传递。两种不同的LnVO4（Ln=Y／Gd）基质对发光性质也有一定的影响。小浓度Bi^3＋的掺人可以明显提高YVO4：Er^3＋／Nd^3＋的近红外发光强度。     

Emission characteristics of inorganic/organic hybrid white-light phosphor

A white-light light-emitting diode (LED) was successfully fabricated by converting near-UV LED emission (390–420 nm) with a new inorganic/organic hybrid phosphor. This new white-light phosphor consisted of three fluorescence materials; two strontium aluminates based with lanthanide oxides, SrAl₂O₄:Eu²⁺ (for green (520 nm) emission) and Sr₄Al₁₄O₂₅:Eu²⁺ (for blue (490 nm) emission) and a new organic Eu metal complex, Eu(BTFA)₃phen (for red (614 nm) emission). These materials have good absorption in the 300–500-nm range and have high quantum efficiencies (4.7–24.5%). The white phosphor has a CIE value of (0.321, 0.365). PACS 42.70.-aj; 78.40.-q; 78.55.-m; 81.05.Lg     

Using multiple short-end injections to develop fast electrophoretic separations--applications in iodide analysis

The aim of this study was to develop a fast CE separation method by using multiple short-end injections in a capillary coated with quaternary ammonium chitosan (HACC), in order to determine the iodide content of pharmaceutical formulations. The BGE was composed of 20 mM tris(hydroxymethyl)aminomethane and 11 mM hydrochloric acid, at pH 8. The internal standard used was thiocyanate. Separations were performed in a fused silica capillary (32 cm total length, 8.5 cm effective length and 50 μm i.d.) coated with HACC and direct UV detection at 220 nm. EOF was modified by flushing the capillary with polymeric solution, resulting in a semi-permanent coating of controlled and stable EOF. The EOF was anodic at pH 8. Different strategies, using single and multiple injection short-end configurations, were studied to develop a CE method that resulted in a maximum number of iodide samples analyzed per hour: one plug and flush (Sflush) 35 samples/h, one plug without flush (SWflush) 76 samples/h, four plugs and flush (Mflush) 61 samples/h, and four plugs without flush (MWflush) 80 samples/h. Using the multiple injection configuration, it was possible to inject up to four plugs using spacer electrolytes with good separation efficiency and selectivity. The voltage application time needed to separate the eight peaks (iodide and thiocyanate) with MWflush was only 12s. The method was validated and samples were analyzed using MWflush. Good linearity (R(2)>0.999); a limit of detection 0.4 mg L(-1); intermediate precision better than 3.8% (peak area) and recovery in the range of 99-102% were obtained.     

Synthesis and light‐emitting properties of platinum‐containing oligoynes and polyynes derived from oligo(fluorenyleneethynylenesilylene)s

A series of blue‐light‐emitting oligo(fluorenyleneethynylenesilylene)s (OFESs) of the general formula HC?CRC?C(EC?CRC?C)_mEC?CRC?CH (E = SiPh₂, SiMe₂, or SiMe₂? SiMe₂; m = 0–2; R = 9,9‐dihexylfluorene‐2,7‐diyl) and their phosphorescent platinum‐containing oligoynes and polyynes were synthesized and characterized. The solution properties and regiochemical structures of this new structural class of organosilicon‐based polyplatinayne polymers {trans‐[? Pt(PBu₃)₂C ?CRC?C(EC?CRC?C)_mEC?CRC?C? ]_n} were studied with IR and NMR (¹H, ¹³C, ²⁹Si, and ³¹P) spectroscopy. The optical absorption and photoluminescence spectra of these metallopolymers were examined and compared with their discrete oligomeric model complexes. Our studies led to a novel approach of using the sp³‐silyl moiety as a conjugation interrupter to limit the effective conjugation length in metal polyynes, which could boost the phosphorescence decay rates essential for light‐energy harvesting from the triplet excited state. The influence of the heavy platinum atom and the group 14 silyl unit possessing different side‐group substituents on the thermal and phosphorescence properties was investigated in detail. We also established the goal of studying the evolution of the lowest singlet and triplet excited states with chain length m of OFESs and the nature of E in these metallopolymers. This work indicated that the phosphorescence emission efficiency harnessed through the heavy‐atom effect of platinum in the main chain did not change very much with oligomer chain length m but generally decreased with the E group in the order SiMe₂ > SiMe₂? SiMe₂ > SiPh₂. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4804–4824, 2006     

An organic p-type dopant with high thermal stability for an organic semiconductor

To overcome the thermal instability of a p-doped organic hole transporting layer using the state-of-the-art p-type dopant, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, a potent electron accepter, 3,6-difluoro-2,5,7,7,8,8-hexacyanoquinodimethane, has been found to possess superior thermal stability and proved to be an excellent p-type dopant.     

Two-Higgs-doublet type-II and -III models and $$t\rightarrow c h$$ at the LHC

We study the constraints of the generic two-Higgs-doublet model (2HDM) type-III and the impacts of the new Yukawa couplings. For comparisons, we revisit the analysis in the 2HDM type-II. To understand the influence of all involving free parameters and to realize their correlations, we employ a \(\chi \)-square fitting approach by including theoretical and experimental constraints, such as the S, T, and U oblique parameters, the production of standard model Higgs and its decay to \(\gamma \gamma \), \(WW^*/ZZ^*\), \(\tau ^+\tau ^-\), etc. The errors of the analysis are taken at 68, 95.5, and \(99.7~\%\) confidence levels. Due to the new Yukawa couplings being associated with \(\cos (\beta -\alpha )\) and \(\sin (\beta -\alpha )\), we find that the allowed regions for \(\sin \alpha \) and \(\tan \beta \) in the type-III model can be broader when the dictated parameter \(\chi _F\) is positive; however, for negative \(\chi _F\), the limits are stricter than those in the type-II model. By using the constrained parameters, we find that the deviation from the SM in \(h\rightarrow Z\gamma \) can be of \(\mathcal{O}(10~\%)\). Additionally, we also study the top-quark flavor-changing processes induced at the tree level in the type-III model and find that when all current experimental data are considered, we get \(Br(t\rightarrow c(h, H) )< 10^{-3}\) for \(m_h=125.36\) and \(m_H=150\) GeV, and \(Br(t\rightarrow cA)\) slightly exceeds \(10^{-3}\) for \(m_A =130\) GeV.     

Steps along the path to dihydrogen activation at [FeFe] hydrogenase structural models: dependence of the core geometry on electrocatalytic proton reduction

Differences in the rate of electrocatalytic proton reduction by Fe2(mu-PPh2)2(CO)6, DP, and the linked phosphido-bridged analogue Fe2(mu,mu-PPh(CH2)3PPh)(CO)6, 3P, suggest that dihydrogen elimination proceeds through a bridging hydride. The reaction path was examined using electrochemical, spectroscopic, and in silico studies where reduction of 3P gives a moderately stable monoanion [Kdisp(3P-) = 13] and a distorted dianion. The monomeric formulation of 3P- is supported by the form of the IR and EPR spectra. EXAFS analysis of solutions of 3P, 3P-, and 3P2- indicates a large increase in the Fe-Fe separation following reduction (from 2.63 to ca. 3.1-3.55 A). DFT calculations of the 3P, 3P-, 3P2- redox series satisfactorily reproduce the IR spectra in the nu(CO) region and the crystallographic (3P) and EXAFS-derived Fe-Fe distances. Digital simulation of the electrocatalytic response for proton reduction indicates a low rate of dihydrogen evolution from the two-electron, two-proton product of 3P (H23P), with more rapid dihydrogen evolution following further reduction of H23P. Because dihydrogen evolution is not observed upon formation of H2DP, dihydrogen evolution at the two-electron-reduced level does not involve protonation of a hydridic Fe-H ligand. The rates of dihydrogen elimination from H2DP, H23P, and H2Fe2(mu,mu-S(CH2)3S)(CO)6 (H23S) are related to the DFT-calculated H-H distances [H23S (1.880 A) < H23P (2.064 A) < H2DP (3.100 A)], and this suggests a common reaction path for the thiolato- and phosphido-bridged diiron carbonyl compounds.     

Synthesis and structure-linear and structure-nonlinear optical properties of multi-dipolar zigzag oligoaryleneethynylenes

A novel series of monodisperse, multi-dipolar zigzag oligoaryleneethynylenes DA(n) and D-Ar-A(n), bearing electron-donating dibenzothiophene and electron-accepting dibenzothiophene dioxide as arenes, with up to six charge-transfer (dipolar) units have been designed and synthesized by palladium-catalyzed Sonogashira coupling reactions. The linear and nonlinear optical properties of these multi-dipolar oligoaryleneethynylenes can easily be modified or enhanced by incorporating/extending with various central aryleneethynyl moieties such as phenylethynyl, oligo(9,9-dibutylfluorenyl)ethynyl, and oligothienylethynyl within the donor-acceptor units. Interestingly, the absorption and emission of these zigzag oligoaryleneethynylenes are not dependent on the number of covalently linked dipolar chromophores; however, the fluorescence quantum efficiencies consistently decrease with increased number of covalently linked dipolar units. These zigzag oligoaryleneethynylenes exhibit a linear increase in the two-photon absorption (TPA) cross-sections with increased number of covalently linked dipolar units without red-shifting the absorption and emission spectra. In addition, very large TPA cross-sections in the femtosecond regime (sigma(800) = 1306 GM in DMF or sigma(750) = 1522 GM in CH(2)Cl(2)) were obtained for D-TF-A(4) despite the moderate strength of the donor-acceptor pair. Our results suggest that the TPA properties of these zigzag oligoaryleneethynylenes including TPA wavelength and TPA cross-section can easily be tuned by means of modifying the central aryleneethynylene units and increasing the number of dipolar units, respectively. This approach provides an alternative means to tune or enhance the TPA cross-section at a specific wavelength.     

A novel electrochemical approach for fabrication of photoluminescent erbium-doped porous silicon

21 /cm³. After this new ECD treatment, PS:Er was found to emit much more intense room-temperature visible photoluminescence than both the porous silicon control and the PS:Er prepared by constant-current ECD. Room-temperature IR photoluminescence around 1.54 μm was observed for the first time without any post-doping annealing. Received: 3 September 1998/Accepted: 9 September 1998     

Processing and morphological development of carbon black filled conducting blends using a binary host of poly(styrene co‐acrylonitrile) and poly(styrene)

The effects of host/filler interactions, processing, and morphological development of low percolation threshold (Φ_c) conducting blends were investigated. It was found that the value of Φ_c was dramatically reduced by the isolation of the carbon black (CB) conducting filler at the cocontinuous interface of a binary poly(styrene) (PS) and poly(styrene co‐acrylonitrile) (SAN) insulating host, resulting in a multiple percolation effect. Accumulation of the filler at the interface was possible due to the incompatibility of the CB filler with the PS phase and partial compatibility with the SAN phase. The best results were obtained by initially dispersing the CB in the PS phase during melt‐ blending, followed by the addition of the SAN phase. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3106–3119, 2000