1000 resultados para LU(III)


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The electrochemical characteristics of a series of heteroleptic tris(phthalocyaninato) complexes with identical rare earths or mixed rare earths (Pc)M(OOPc)M(OOPc) [M = Eu...Lu, Y; H2Pc = unsubstituted phthalocyanine, H2(OOPc) = 3,4,12,13,21,22,30,31-octakis(octyloxy)phthalocyanine] and (Pc)Eu(OOPc)Er(OOPc) have been recorded and studied comparatively by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) in CH2Cl2 containing 0.1 M tetrabutylammonium perchlorate (TBAP). Up to five quasi-reversible one-electron oxidations and four one-electron reductions have been revealed. The half-wave potentials of the first, second and fifth oxidations depend on the size of the metal center, but the fifth changes in the opposite direction to that of the first two. Moreover, the difference in redox potentials of the first oxidation and first reduction for (Pc)M(OOPc)M(OOPc), 0.85−0.98 V, also decreases linearly along with decreasing rare earth ion radius, clearly showing the rare earth ion size effect and indicating enhanced π−π interactions in the triple-deckers connected by smaller lanthanides. This order follows the red-shift seen in the lowest energy band of triple-decker compounds. The electronic differences between the lanthanides and yttrium are more apparent for triple-decker sandwich complexes than for the analogous double-deckers. By comparing triple-decker, double-decker and mononuclear [ZnII] complexes containing the OOPc ligand, the HOMO−LUMO gap has been shown to contract approximately linearly with the number of stacked phthalocyanine ligands.

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The electrochemistry of homoleptic substituted phthalocyaninato rare earth double-decker complexes M(TBPc)2 and M(OOPc)2 [M = Y, La...Lu except Pm; H2TBPc = 3(4),12(13),21(22),30(31)-tetra-tert-butylphthalocyanine, H2OOPc = 3,4,12,13,21,22,30,31-octakis(octyloxy)phthalocyanine] has been comparatively studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) in CH2Cl2 containing 0.1 M tetra-n-butylammonium perchlorate (TBAP). Two quasi-reversible one-electron oxidations and three or four quasi-reversible one-electron reductions have been revealed for these neutral double-deckers of two series of substituted complexes, respectively. For comparison, unsubstituted bis(phthalocyaninato) rare earth analogues M(Pc)2 (M = Y, La...Lu except Pm; H2Pc = phthalocyanine) have also been electrochemically investigated. Two quasi-reversible one-electron oxidations and up to five quasi-reversible one-electron reductions have been revealed for these neutral double-decker compounds. The three bis(phthalocyaninato)cerium compounds display one cerium-centered redox wave between the first ligand-based oxidation and reduction. The half-wave potentials of the first and second oxidations and first reduction for double-deckers of the tervalent rare earths depend on the size of the metal center. The difference between the redox potentials of the second and third reductions for MIII(Pc)2, which represents the potential difference between the first oxidation and first reduction of [MIII(Pc)2]−, lies in the range 1.08−1.37 V and also gradually diminishes along with the lanthanide contraction, indicating enhanced π−π interactions in the double-deckers connected by the smaller, lanthanides. This corresponds well with the red-shift of the lowest energy band observed in the electronic absorption spectra of reduced double-decker [MIII(Pc′)2]− (Pc′ = Pc, TBPc, OOPc).

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We report experiments on high de current stressing in commercial III-V nitride based heterojunction light-emitting diodes. Stressing currents ranging from 100 mA to 200 mA were used. Degradations in the device properties were investigated through detailed studies of the current-voltage (I-V) characteristics, electroluminescence, deep-level transient Fourier spectroscopy and flicker noise. Our experimental data demonstrated significant distortions in the I-V characteristics subsequent to electrical stressing. The room temperature electro-luminescence of the devices exhibited a 25% decrement in the peak emission intensity. Concentration of the deep-levels was examined by deep-level transient Fourier spectroscopy, which indicated an increase in the density of deep-traps from 2.7 x 10(13) cm(-3) to 4.2 x 10(13) cm(-3) at E-1 = E-C - 1.1 eV. The result is consistent with our study of 1/f noise, which exhibited up to three orders of magnitude increase in the voltage noise power spectra. These traps are typically located at energy levels beyond the range that can be characterized by conventional techniques including DLTS. The two experiments, therefore, provide a more complete picture of trap generation due to high dc current stressing.

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We report experiments on hot-electron stressing in commercial III-V nitride based heterojunction fight-emitting diodes. Stressing currents ranging from 100 mA to 200 mA were used. Degradations in the device properties were investigated through detailed studies of the I-V characteristics, electroluminescence, Deep-Level Transient Fourier Spectroscopy and flicker noise. Our experimental data demonstrated significant distortions in the I-V characteristics. The room temperature electroluminescence of the devices exhibited 25% decrement in the peak emission intensity. Concentration of the deep-levels was examined by measuring the Deep-Level Transient Fourier Spectroscopy, which indicated an increase in the density of deep-traps from 2.7 x 10(13) cm(-3) to 4.21 x 10(13) cm(-3) at E-1 = E-C - 1.1eV. The result is consistent with our study of 1/f noise, which exhibited up to three orders of magnitude increase in the voltage noise power spectra. Our experiments show large increase in both the interface traps and deep-levels resulted from hot-carrier stressing.

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本文包括标题配合物的结构和振动光谱两部分,共涉及了M(DMP)_n {n=2.3, M=2a, Nd, Cu. Zn}, Ln(DPP)_3{2n=2a-2u, Y}和Ln(BBP)_3 {Ln=La-Lu. Y}三类三十四个配合物。在结构方面,首次测定了Zn(DMP)_2和Cu(DMP)_2呈现出链状配位高聚结构,而La(DMP)_3, La(DMP)_3则为平面网状配位高聚结构。在Zn(DMP)_2, La(DMP)_3和Nd(DMP)_3中,配体以对称“O-P-O”桥键与金属原子配位,在相邻金属原子间形成双桥键。在Zn(DMP)_2中,每个Zn原子通过“O-P-O”双桥键与另两个Zn原子连接,Zn原子配位数为4,配位多面体为四面体构型;在La(DMP)_3和Nd(DMP)_3中,每个稀土原子通过“O-P-O”双桥键与另外三个稀土原子相连接,稀土原子的配位数为6,配位多面体LnO_6为八面体构型。在Cu(DMP)_3中, 配体以对称和非对称“O-P-O”桥键两种形式存在,其中非对称配位的配体形成为“Cu-O-P_O-Cu"-Cu,在铜原之间形成了一个单氧桥键。每个Cu原子通过双“O-P-O”桥键以及双单氧原子桥键与另外三个Cu原子相连接,Cu原子配位数为5,配位多面体为四角锥构型。在振动光谱方面,得到了上述配合物较为完整的光谱数据,并对主要光谱带进行了归属,如V_(M-O), V_(PO_2), V_(P-O(c)),VC-O, VP-C及σ_PO_2等。在稀土配合物中,稀土配位键的伸缩振动V_(vn-o)位于250cm~(-1)附近。V_(Cu)和V_(Zn-o),在Cu(DMP)_2和Zn(DMP)_2中,分别为(412cm~(-1), 370cm~(-1))和(393cm~(-1), 386cm~(-1))。V_(as)PO_2和V_sPO_2,在配合物振动光谱中,分别在1130-1249cm~(-1)区和1084-1156cm~(-1)区。在稀土配合物中,VL_(n-o), V_(as)PO_2频率值,随镧系收缩逐渐递增。在Cu(DMP)_2红外谱中,非对称配体和对称配体的V_(as)PO_2和V_sPO_2, 分别为(1249cm~(-1),1156cm~(-1))及(1177cm~(-1),1090cm~(-1)),其劈裂值△V(V_(as)PO_2-V_sPO_2)为93cm~(-1)和87cm~(-1)。通过对配合物的常温和低温红外光谱的比较,确认了La(DMP)3和Nd(DMP)_3的176cm~(-1)、Ln(DPP)_3和Ln(BBP)_3的150cm~(-1)附近吸收为晶格振动。Ln(DPP)_3、Ln(BBP_3)的光谱性质与Ln(DMP)_3相似,我们认为它们之间具有相同的骨架结构-平面网状配位高聚结构。

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We successfully prepared a new kind of thermoresponsive and fluorescent complex of Tb(III) and PNIPAM-g-P(NIPAM-co-St) (PNNS) core-shell nanoparticle. It was found that Tb(III) mainly bonded to 0 of the carbonyl groups of PNNS, forming the novel (PNIPAM-g-P(NIPAM-co-St))-Tb(III) (PNNS-Tb(III)) complex. The maximum emission intensity of the complex at 545 nm is enhanced about 223 times comparing to that of the pure Tb(III). The intramolecular energy transfer efficiency from PNNS to Tb(III) reaches 50%. When the weight ratio of Tb(III) and the PNNS-Tb(III) complex is 1.2 wt.%, the enhancement of the emission fluorescence intensity at 545 nm is highest.

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Neuromelanin is a complex polymer pigment found primarily in the dopaminergic neurons of the human substantia nigra, whose composition is complex including production of dopamine auto-oxidation, glutathione and a variety of amino acid. Neuromelanin forms stable complex with iron (111). We observed that 5,6-dihydroxyindole and its ramification possessed strong ability of chelating iron (111), and they are the production of dopamine auto-oxidation under physiological pH condition. In the present Of L-Cysteine, the relative yields of electrochemical oxidation of dopamine also had strong ability of chelating iron (111). The experimental results suggest that 5,6-dihydroxyindole and 5-S-cysteineldopamine play important roles in the process of synthetic neuromelanin chelating iron (111).

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A multiphase model of metal ion speciation in human interstitial fluid was constructed and the effect of Pr(III) on Ca(II) speciation was studied. Results show that free Ca2+, [Ca(HCO3)], and [Ca(Lac)] are the main species of Ca(II). Because of the competition of Pr(III) for ligands with Ca(II), the percentages of free Ca2+, [Ca(Lac)], and [Ca(His)(Thr)H-3] increase gradually and the percentages of CaHPO4(aq) and [Ca(Cit)(His)H-2] decrease gradually with the increase in the total concentration of Pr(III). However, the percentages of [Ca(HCO3)] and CaCO3(aq) first increase and then begin to decrease when the total concentration of Pr(III) exceeds 6.070 x 10(-4) M.

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A multi-phase model of Pr(III) speciation in human interstitial fluid was constructed and insoluble Pr(III) speciation was studied. When the total concentration of Pr(III) is below 8.401E-10 mol/L, soluble Pr(III) species are main species. With rising the total concentration of Pr(III), Pr(III) is firstly bound to phosphate to form precipitate of PrPO4, then bound to carbonate and another precipitate of Pr-2(CO3)(3) was obtained. When the total concentration is between 1.583E-9 mol/L and 4.000E-3 mol/L, the insoluble species are predominant Pr(III) species.

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Crystallization and melting behavior of short ethylene sequence of metallocene ethylene/alpha -olefin copolymer with high comonomer content have been studied by standard DSC and modulated-temperature differential scanning calorimetry (M-TDSC) technique. In addition to high temperature endotherm around 120 degreesC, a low temperature endotherm is observed at lower temperatures (40-80 degreesC), depending on time and temperature of isothermal crystallization. The peak position of the low temperature endotherm T-m(low) varies linearly with the logarithm of crystallization time and the slope, D, decreases with increasing crystallization temperature T-c. The T-m(low) also depends on the thermal history before the crystallization at T-c, and an extrapolation of T-m(low) (30.6 degreesC) to a few seconds has been obtained after two step isothermal crystallization before the crystallization at 30 degreesC. The T-m(low) is nearly equal to T-c, and it indicates that the initial crystallization at low temperature is nearly reversible. Direct evidence of conformational. entropy change of secondary crystallization has been obtained by using M-TDSC technique. Both the M-TDSC result and the activation energy analysis of temperature dependence suggest that crystal perfection process and conformational entropy decreasing in residual amorphous co-exist during secondary crystallization.

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Rare earth(III)-histidine (His)- tryptophane (Trp). Ca(II)-His-Trp and Zn(II)-His-Trp systems were studied by potentiometric titration and computer simulation under physiological conditions. The species of the systems and their stability constants were determined. The distributions of species of rare earth(III), Ca(II) and Zn(II) were discussed.

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The insoluble species of Gd (III) in human blood plasma were investigated by computer simulation. The distribution of the Gd (I) species was obtained. It was found that most of the Gd (III) ions were bound to phosphate to form precipitate GdPO4 at the concentration of 1. 000 x 10(-7) mol/L and when the concentration of the Gd (III) increased to 3. 750 x 10(-4) mol/L, in excess of the concentration of phosphate, the Gd (III) ions were bound to carbonate to form another kind of precipitate, Gd-2 (CO3)(3).

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The solution structures of diamagnetic lanthanide (III) complexes of DTPA-BIN (Ln = La, Y, Lu, Sc) have been investigated by H-1 NMR, C-13 NMR and 2D NMR. For each complex, two or more species of asymmetric conformations with little distinction were identified at room temperature. And their solution structures vary with the radius of the central metals. NMR spectra support the hypothesis that Sc3+ with smaller radius formed an eight-coordinated structure with DTPA-BIN, La3+ with larger radius formed nine- or ten-coordinated structures with DTPA-BIN, and Y (DTPA-BIN) and Lu (DTPA-BIN) had nine-coordinated solution structures. The solution structure of Gd (DTPA-BIN) was obtained from the similarity of radius between Gd3+ and Y3+, which is a nine-coordinated structure formed by three nitrogens, three acetate oxygens, two acetyl oxygens, one water molecule and a gadolinium(III) cation.

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A multi-phase model was developed and Tb(III) speciation in human blood plasma was studied. At a concentration below 3.744x 10(-4) mol/L (or at the concentration), Tb(III) is mostly bound to phosphate to form precipitate of TbPO4. As the concentration of Tb(III) increases, phosphate is exceeded and another kind of precipitate of Tb-2(CO3)(3) appears. Among soluble Tb(III) species, Tb(III) mainly distribute in [Tb (Tf)] at low concentration and in [Tb (HSAA, [Tb-2 (Tf)], [Th (IgG)], [Tb (Lactate)](2+), [Tb (CitArgH)] and free Tb(III) at high concentration.