Ternary lanthanide (Er3+, Nd3+, Yb3+, Sm3+, Pr3+) complex-functionalized mesoporous SBA-15 materials that emit in the near-infrared range

The tertiary lanthanide complexes [Ln(hfth)(3)phen] (Ln=Er, Nd, Yb, Sm) and [Pr(tfnb)(3)phen] have been Successfully covalently attached in the ordered SBA-15 mesoporous materials via a functionalized 1,10-phenanthroline group 5-(N,N-bis-3-(triethoxysilyl)propyl)ureyl-1,10-phenanthroline (Phen-Si). The derivative materials [denoted as Ln(hfth)(3)phen-S15 and Pr(tfnb)(3)phen-S15; Ln=Er, Yb, Nd, Sm; hfth=4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)hexane-1,3-dionate; tfnb=4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedionate] were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), and N-2 adsorption/desorption.

Covalent linking of near-infrared luminescent ternary lanthanide (Er3+, Nd3+, Yb3+) complexes on functionalized mesoporous MCM-41 and SBA-15

The near-infrared (NIR) luminescent lanthanide ions, such as Er(III), Nd(III), and Yb(III), have been paid much attention for the potential use in the optical communications or laser systems. For the first time, the NIR-luminescent Ln(dbm)(3)phen complexes have been covalently bonded to the ordered mesoporous materials MCM-41 and SBA-15 via a functionalized phen group phen-Si (phen-Si = 5-(N,N-bis-3-(triethoxysilyl)propyl)ureyl-1,10-phenanthroline; dbm = dibenzoylmethanate; Ln = Er, Nd, Yb). The synthesis parameters X = 12 and Y = 6 h (X denotes Ln(dbM)(3)(H2O)(2)/phen-MCM-41 molar ratio or Ln(dbM)(3)(H2O)(2)/phenSBA-15 molar ratio and Y is the reaction time for the ligand exchange reaction; phen-MCM-41 and phenSBA-15 are phen-functionalized MCM-41 and SBA-15 mesoporous materials, respectively) were selected through a systematic and comparative study. The derivative materials, denoted as Ln(dbM)(3)phen-MCM-41 and Ln(dbm)(3)phen-SBA-15 (Ln = Er, Nd, Yb), were characterized by powder X-ray diffraction, nitrogen adsorption/desorption, Fourier transform infrared (FT-IR), elemental analysis, and fluorescence spectra. Upon excitation of the ligands absorption bands, all these materials show the characteristic NIR luminescence of the corresponding lanthanide ions through the intramolecular energy transfer from the ligands to the lanthanide ions.

Crystal field splitting of Nd3+ ion and chemical bonds on the host crystals

In terms of the theory of chemical bonds on complex crystals(CBCC), the crystal structure and coordination, the chemical bond parameters of a group of ABO(4)-type crystals were calculated in detail, The results show that the relation between the crystal field splitting of Nd3+ ion and the covalency of the crystal is linear.

Electrochemical behavior of Nd3+ and Ho3+ in LiCl-KCl eutectic melt

The electrochemical behavior of Nd3+ and Ho3+ ions on molybdenum electrode in the LiCl-KCl eutectic melts has been studied by cyclic voltammetry and open-circuit potentiometry. The results show that the reduction process of Nd3+ and Ho3+ ions on molybdenum electrode is one-step three electron reversible reaction. The diffusion coefficients of Nd3+ and Ho3+ ions are 1.13 x 10(-6) cm(2).s(-1)(450 degrees C) and 2.142 x 10(-5) cm(2).s(-1)(450 degrees C), respectively. The measured standard electrode potential of Ho3+/Ho is 2.987 V(vs. Cl/Cl-), being more negative than the theoretical one, the reason of which is also discussed.

Identification of the mitochondrial ND3 subunit as a structural component involved in the active/deactive enzyme transition of respiratory complex I

Mitochondrial complex I (NADH: ubiquinone oxidoreductase) undergoes reversible deactivation upon incubation at 30-37 degrees C. The active/deactive transition could play an important role in the regulation of complex I activity. It has been suggested recently that complex I may become modified by S-nitrosation under pathological conditions during hypoxia or when the nitric oxide: oxygen ratio increases. Apparently, a specific cysteine becomes accessible to chemical modification only in the deactive form of the enzyme. By selective fluorescence labeling and proteomic analysis, we have identified this residue as cysteine-39 of the mitochondrially encoded ND3 subunit of bovine heart mitochondria. Cysteine-39 is located in a loop connecting the first and second transmembrane helix of this highly hydrophobic subunit. We propose that this loop connects the ND3 subunit of the membrane arm with the PSST subunit of the peripheral arm of complex I, placing it in a region that is known to be critical for the catalytic mechanism of complex I. In fact, mutations in three positions of the loop were previously reported to cause Leigh syndrome with and without dystonia or progressive mitochondrial disease.

ND3, ND1 and 39 kDa subunits are more exposed in the de-active form of bovine mitochondrial complex I

An intriguing feature of mitochondrial complex I from several species is the so-called A/D transition, whereby the idle enzyme spontaneously converts from the active (A) form to the de-active (D) form. The A/D transition plays an important role in tissue response to the lack of oxygen and hypoxic deactivation of the enzyme is one of the key regulatory events that occur in mitochondria during ischaemia. We demonstrate for the first time that the A/D conformational change of complex I does not affect the macromolecular organisation of supercomplexes in vitro as revealed by two types of native electrophoresis. Cysteine 39 of the mitochondrially-encoded ND3 subunit is known to become exposed upon de-activation. Here we show that even if complex I is a constituent of the I + III + IV (S) supercomplex, cysteine 39 is accessible for chemical modification in only the D-form. Using lysine-specific fluorescent labelling and a DIGE-like approach we further identified two new subunits involved in structural rearrangements during the A/D transition: ND1 (MT-ND1) and 39 kDa (NDUFA9). These results clearly show that structural rearrangements during de-activation of complex I include several subunits located at the junction between hydrophilic and hydrophobic domains, in the region of the quinone binding site. De-activation of mitochondrial complex I results in concerted structural rearrangement of membrane subunits which leads to the disruption of the sealed quinone chamber required for catalytic turnover.

Time-resolved study electronic and thermal contributions to the nonlinear refractive index of Nd3+: SBN laser crystals

The propagation of an optical beam through dielectric media induces changes in the refractive index, An, which causes self-focusing or self-defocusing. In the particular case of ion-doped solids, there are thermal and non-thermal lens effects, where the latter is due to the polarizability difference, Delta alpha, between the excited and ground states, the so-called population lens (PL) effect. PL is a pure electronic contribution to the nonlinearity, while the thermal lens (TL) effect is caused by the conversion of part of the absorbed energy into heat. In time-resolved measurements such as Z-scan and TL transient experiments, it is not easy to separate these two contributions to nonlinear refractive index because they usually have similar response times. In this work, we performed time-resolved measurements using both Z-scan and mode mismatched TL in order to discriminate thermal and electronic contributions to the laser-induced refractive index change of the Nd3+-doped Strontium Barium Niobate (SrxBa1-xNb2O6) laser crystal. Combining numerical simulations with experimental results we could successfully distinguish between the two contributions to An. (C) 2007 Elsevier B.V. All rights reserved.

A route to obtain Gd2O3:Nd3+ with different particle size

Funda����o de Amparo �� Pesquisa do Estado de S��o Paulo (FAPESP)

Dielectric and impedance properties of Nd3/2Bi3/2Fe5O12 ceramics

The polycrystalline sample of Nd3/2Bi3/2Fe5O12 was prepared by a high- temperature solid-state reaction technique. Preliminary X-ray structural analysis exhibits the formation of a single-phase tetragonal structure at room temperature. Microstructural analysis by scanning electron microscopy shows that the sintered sample has well defined grains. These grains are distributed uniformly throughout the surface of the sample. Detailed studies of dielectric response at various frequencies and temperatures exhibit a dielectric anomaly at 400 A degrees C. The electrical properties (impedance, modulus and conductivity) of the material were studied using a complex impedance spectroscopy technique. These studies reveal a significant contribution of grain and grain boundary effects in the material. The frequency dependent plots of modulus and the impedance loss show that the conductivity relaxation is of non-Debye type. Studies of electrical conductivity with temperature demonstrate that the compound exhibits Arrhenius-type of electrical conductivity. Study of ac conductivity with frequency suggests that the material obeys Jonscher's universal power law.

Ytterbium-induced energy-transfer upconversion enhancement in Nd3+/Pr3+-codoped PbGeO3-PbF2-CdF2 glass excited at 810nm

The effect of ytterbium ions upon energy transfer (ET) excited upconversion emission in Nd3+/Pr3+ -codoped PbGeO3-PbF2-CdF2 glass under 810 nm diode laser excitation is investigated. The results revealed that the presence of Yb3+ ions in the Nd3+/Pr3+-doped sample yields a fourfold enhancement in the visible and near infrared upconversion luminescence. The dependence of the upconversion process upon the excitation power, Nd3+, and Yb3+ concentrations is examined. The results indicated that ytterbium plays a major role in the ET upconversion process by bridging the 810nm neodymium excitation to praseodymium ions. The population of the Pr3+ ions P-3(0) emitting level was accomplished through a multi-ion interaction involving ground-state and excited-state absorption of pump photons at 810 nm by the Nd3+ followed by successive ET involving the Nd3+-Yb3+ and Yb3+-Pr3+ pairs. There is also direct ET Nd3+-Pr3+. (c) 2005 Elsevier B.V. All rights reserved.

Sensitized thulium blue upconversion emission in Nd3+/Tm3+/Yb3+ triply doped lead and cadmium germanate glass excited around 800 nm

Bright blue upconversion emission by thulium ions in PbGeO3-PbF2-CdF2 glass triply doped with Nd3+-Tm3+-Yb3+ under diode laser excitation around 800 nm is reported. The results revealed that the Nd3+/Tm3+/Yb3+-codoped sample generated ten times more 475 nm blue upconversion fluorescence than the Yb3+-sensitized Tm3+-doped one, under the same excitation power. The upconversion process also showed a strong dependence upon the Yb3+ concentration. The results also indicated that the neodymium ions played a major role in the upconversion process by transfering the 800 nm excitation to thulium ions. The population of the Tm3+ ions (1)G(4) emitting level was accomplished through a multiion interaction involving ground-state absorption of pump photons around 800 nm by the Nd3+(I-4(9/2)-->H-2(9/2), F-4(5/2)) and Tm3+(H-3(6)-->F-3(4)) ions followed by energy-transfer processes involving the Nd3+-Yb3+(F-4(3/2), F-2(7/2)-->I-4(11/2), F-2(5/2)) and Yb3+-Tm3+(F-2(5/2), F-3(4)-->F-2(7/2), (1)G(4)) pairs. (C) 2003 American Institute of Physics.

Optical properties and energy transfer processes in (Tm3+, Nd3+) doped tungstate fluorophosphate glass

We investigate the linear optical properties and energy transfer processes in tungstate fluorophosphate glass doped with thulium (Tm3+) and neodymium (Nd3+) ions. The linear absorption spectra from 370 to 3000 nm were obtained. Transitions probabilities, radiative lifetimes, and transition branching ratios were determined using the Judd-Ofelt [Phys. Rev. 127, 750 (1962); J. Chem. Phys. 37, 511 (1962)] theory. Frequency up-conversion to the blue region and fluorescence in the infrared were observed upon pulsed excitation in the range of 630-700 nm. The excitation spectra of the luminescence were obtained to understand the origin of the signals. The temporal decay of the fluorescence was measured for different concentrations of the doping ions. Energy transfer rates among the Tm3+ and Nd3+ ions were also determined.

Raman scattering, differential scanning calorimetry and Nd3+ spectroscopy in alkali niobium tellurite glasses

Alkali niobium tellurite glasses have been prepared and some of their properties measured by differential scanning calorimetry and Raman scattering. The vitreous domain was established in the pseudo ternary phases diagram for the system TeO2-Nb2O5-(0.5K(2)O-0.5Li(2)O). Raman scattering shows that for samples in the TeO2 rich part of the phase diagram the vitreous structure is composed essentially of (TeO4) units connected by the vertices, as in the alpha-TeO2 crystal. The addition of alkali and niobium oxides causes depolymerization to occur with structures composed essentially of (TeO3) and (NbO6) units. Samples with the composition (mol%) 80TeO(2)-10Nb(2)O(5)-5K(2)O-5Li(2)O, stable against crystallization, were prepared containing up to 10% mol Nd3+. The addition of this oxide increases the rigidity of the vitreous network shifting characteristic temperatures to higher temperatures. For the 10% Nd3+ sample amorphous phase separation is assumed to exist from the observation of two glass transition temperatures. Spectroscopic properties such as Judd-Ofelt Omega(lambda) intensity parameters, radiative emission probabilities, and induced emission cross sections were calculated. From these results and also from the emission quenching observed as a function of Nd3+ concentration, we suggest that these glasses could be utilized in optical amplifying devices. (C) 1999 Elsevier B.V. B.V. All rights reserved.