Efficient Phosphodiester Hydrolysis by Luminescent Terbium(III) and Europium(III) Complexes

The synthesis and structures of two new isostructural mononuclear [Ln(L)(NO(3))(H(2)O)(3)](NO(3))(2) complexes, with Ln = Tb (complex 1) and Eu (complex 2), which display high activity in the hydrolysis of the substrate 2,4-bis(dinitrophenyl)phosphate, are reported. These complexes displayed catalytic behavior similar to the mononuclear gadolinium complex [Gd(L)(NO(3))(H(2)O)(3)](NO(3))(2) previously reported by us (lnorg. Chem. 2008, 47, 2919-2921); one hydrolysis reaction in two stages where the diesterase and monoesterase activities could be monitored separately, with the first stage dependent on and the second independent of the complex concentration. Through potentiometric studies, electrospray ionization mass spectrometry (ESI-MS) analysis, and determination of the kinetic behaviors of 1 and 2 in acetonitrile/water solution, the species present in solution could be identified and suggested a dinuclear species, with one hydroxo group, as the most prominent catalyst under mild conditions. The complexes show high activity (k(1)= 7 and 18 s(-1) for 1 and 2, respectively) and catalytic efficiency. Complexes 1 and 2 were found to be active toward the cleavage of plasmid DNA, and complete kinetic studies were carried out. Studies with a radical scavenger (dimethylsulfoxide) confirmed the hydrolytic action of 1 and 2 in the cleavage of DNA. Studies on the incubation of distamycin with plasmid DNA suggested that 1 and 2 are regio-specific, interacting with the minor groove of DNA. These complexes displayed luminescent properties. Complex 1 showed higher emission intensity than 2 due to a more efficient energy transfer between triplet and emission levels of terbium (T -> (5)D(4)), along with nonradiative deactivation mechanisms of the excited states of europium via multiphonon decays and the ligand-to-metal charge transfer state. Lifetime measurements of the (5)D(4) and (5)D(0) excited levels for 1 and 2, respectively, indicated the numbers of coordinated water molecules for the complexes.

Effect of quantum interference on a three-level atom driven by two laser fields

We study the effect of quantum interference on the population distribution and absorptive properties of a V-type three-level atom driven by two lasers of unequal intensities and different angular frequencies. Three coupling configurations of the lasers to the atom are analysed: (a) both lasers coupled to the same atomic transition, (b) each laser coupled to different atomic transition and (c) each laser coupled to both atomic transitions. Dressed stales for the three coupling configurations are identified, and the population distribution and absorptive properties of the weaker field are interpreted in terms of transition dipole moments and transition frequencies among these dressed states. In particular, we find that in the first two cases there is no population inversion between the bare atomic states, but the population can be trapped in a superposition of the dressed states induced by quantum interference and the stronger held. We show that the trapping of the population, which results from the cancellation of transition dipole moments, does not prevent the weaker field to be coupled to the cancelled (dark) transitions. As a result, the weaker field can be strongly amplified on transparent transitions. In the case of each laser coupled to both atomic transitions the population can be trapped in a linear superposition of the excited bare atomic states leaving the ground state unpopulated in the steady state. Moreover, we find that the absorption rate of the weaker field depends on the detuning of the strong field from the atomic resonances and the splitting between the atomic excited states. When the strong held is resonant to one of the atomic transitions a quasi-trapping effect appears in one of the dressed states. In the quasi-trapping situation all the transition dipole moments are different from zero, which allows the weaker field to be amplified on the inverted transitions. When the strong field is tuned halfway between the atomic excited states, the population is completely trapped in one of the dressed states and no amplification is found for the weaker field.

Exact results for a tunnel-coupled pair of trapped Bose-Einstein condensates

A model describing coherent quantum tunnelling between two trapped Bose-Einstein condensates is discussed. It is not well known that the model admits an exact solution, obtained some time ago, with the energy spectrum derived through the algebraic Bethe ansatz. An asymptotic analysis of the Bethe ansatz equations leads us to explicit expressions for the energies of the ground and the first excited states in the limit of weak tunnelling and all energies for strong tunnelling. The results are used to extract the asymptotic limits of the quantum fluctuations of the boson number difference between the two Bose-Einstein condensates and to characterize the degree of coherence in the system.

Computational analysis of quinoxalines N,N-Dioxide and ITS Derivates

A quinoxalina e seus derivativos são uma importante classe de compostos heterocíclicos, onde os elementos N, S e O substituem átomos de carbono no anel. A fórmula molecular da quinoxalina é C8H6N2, formada por dois anéis aromáticos, benzeno e pirazina. É rara em estado natural, mas a sua síntese é de fácil execução. Modificações na estrutura da quinoxalina proporcionam uma grande variedade de compostos e actividades, tais como actividades antimicrobiana, antiparasitária, antidiabética, antiproliferativa, anti-inflamatória, anticancerígena, antiglaucoma, antidepressiva apresentando antagonismo do receptor AMPA. Estes compostos também são importantes no campo industrial devido, por exemplo, ao seu poder na inibição da corrosão do metal. A química computacional, ramo natural da química teórica é um método bem desenvolvido, utilizado para representar estruturas moleculares, simulando o seu comportamento com as equações da física quântica e clássica. Existe no mercado uma grande variedade de ferramentas informaticas utilizadas na química computacional, que permitem o cálculo de energias, geometrias, frequências vibracionais, estados de transição, vias de reação, estados excitados e uma variedade de propriedades baseadas em várias funções de onda não correlacionadas e correlacionadas. Nesta medida, a sua aplicação ao estudo das quinoxalinas é importante para a determinação das suas características químicas, permitindo uma análise mais completa, em menos tempo, e com menos custos.

Effect of surface plasmon resonance in TiO2/Au thin films on the fluorescence of self-assembled CdTe QDs structure

The exceptional properties of localised surface plasmons (LSPs), such as local field enhancement and confinement effects, resonant behavior, make them ideal candidates to control the emission of luminescent nanoparticles. In the present work, we investigated the LSP effect on the steady-state and time-resolved emission properties of quantum dots (QDs) by organizing the dots into self-assembled dendrite structures deposited on plasmonic nanostructures. Self-assembled structures consisting of water-soluble CdTe mono-size QDs, were developed on the surface of co-sputtered TiO2 thin films doped with Au nanoparticles (NPs) annealed at different temperatures. Their steady-state fluorescence properties were probed by scanning the spatially resolved emission spectra and the energy transfer processes were investigated by the fluorescence lifetime imaging (FLIM) microscopy. Our results indicate that a resonant coupling between excitons confined in QDs and LSPs in Au NPs located beneath the self-assembled structure indeed takes place and results in (i) a shift of the ground state luminescence towards higher energies and onset of emission from excited states in QDs, and (ii) a decrease of the ground state exciton lifetime (fluorescence quenching).

A new efficient approach to the direct restricted active space self-consistent field method

An implicitly parallel method for integral-block driven restricted active space self-consistent field (RASSCF) algorithms is presented. The approach is based on a model space representation of the RAS active orbitals with an efficient expansion of the model subspaces. The applicability of the method is demonstrated with a RASSCF investigation of the first two excited states of indole

Electron capture and emission by the Ti acceptor level in GaP

Previously reported results on deep level optical spectroscopy, optical absorption, deep level transient spectroscopy, photoluminescence excitation, and time resolved photoluminescence are reviewed and discussed in order to know which are the mechanisms involved in electron capture and emission of the Ti acceptor level in GaP. First, the analysis indicates that the 3T1(F) crystal¿field excited state is not in resonance with the conduction band states. Second, it is shown that both the 3T2 and 3T1(F) excited states do not play any significant role in the process of electron emission and capture.

Microscopic study of He2-SF6 trimers

The He2-SF6 trimers, in their different He isotopic combinations, are studied in the framework of both the correlated Jastrow approach and the correlated hyperspherical harmonics (CHH) expansion method. The energetics and structure of the He-SF6 dimers are analyzed, and the existence of a characteristic rotational band in the excitation spectrum is discussed, as well as the isotopic differences. The binding energies and the spatial properties of the trimers, in their ground and lowest lying excited states, obtained by the Jastrow ansatz are in excellent agreement with the results of the converged CHH expansion. The introduction of the He-He correlation makes all trimers bound by largely suppressing the short range He-He repulsion. The structural properties of the trimers are qualitatively explained in terms of the shape of the interactions, Pauli principle, and masses of the constituents.

Collective and single-particle excitations of a trapped Bose gas

The density of states of a Bose-condensed gas confined in a harmonic trap is investigated. The predictions of Bogoliubov theory are compared with those of Hartree-Fock theory and of the hydrodynamic model. We show that the Hartree-Fock scheme provides an excellent description of the excitation spectrum in a wide range of energy, revealing a major role played by single-particle excitations in these confined systems. The crossover from the hydrodynamic regime, holding at low energies, to the independent-particle regime is explicitly explored by studying the frequency of the surface mode as a function of their angular momentum. The applicability of the semiclassical approximation for the excited states is also discussed. We show that the semiclassical approach provides simple and accurate formulas for the density of states and the quantum depletion of the condensate.

Landau damping of transverse quadrupole oscillations of an elongated Bose-Einstein condensate

We have studied the interaction between the low-lying transverse collective oscillations and the thermal excitations of an elongated Bose-Einstein condensate by means of perturbation theory. We consider a cylindrical trapped condensate and calculate the transverse elementary excitations at zero temperature by solving the linearized Gross-Pitaevskii equations in two dimensions (2D). We use them to calculate the matrix elements between the thermal excited states and the quasi-2D collective modes. The Landau damping of transverse collective modes is studied as a function of temperature. At low temperatures, the corresponding damping rate is in agreement with the experimental data for the decay of the transverse quadrupole mode, but it is too small to explain the observed slow decay of the transverse breathing mode. The reason for this discrepancy is discussed.

Vortices in atomic Bose-Einstein condensates in the large-gas-parameter region

In this work we compare the results of the Gross-Pitaevskii and modified Gross-Pitaevskii equations with ab initio variational Monte Carlo calculations for Bose-Einstein condensates of atoms in axially symmetric traps. We examine both the ground state and excited states having a vortex line along the z axis at high values of the gas parameter and demonstrate an excellent agreement between the modified Gross-Pitaevskii and ab initio Monte Carlo methods, both for the ground and vortex states.

Ab initio valence-bond cluster model for ionic solids: Alkaline-earth oxides

A linear M-O-M (M=metal, O=oxygen) cluster embedded in a Madelung field, and also including the quantum effects of the neighboring ions, is used to represent the alkaline-earth oxides. For this model an ab initio wave function is constructed as a linear combination of Slater determinants written in an atomic orbital basis set, i.e., a valence-bond wave function. Each valence-bond determinant (or group of determinants) corresponds to a resonating valence-bond structure. We have obtained ab initio valence-bond cluster-model wave functions for the electronic ground state and the excited states involved in the optical-gap transitions. Numerical results are reasonably close to the experimental values. Moreover, the model contains the ionic model as a limiting case and can be readily extended and improved.

Direct Observation of Magnetic Metastability in Individual Iron Nanoparticles

X-ray photoemission electron microscopy combined with x-ray magnetic circular dichroism is used to study the magnetic properties of individual iron nanoparticles with sizes ranging from 20 down to 8 nm. While the magnetocrystalline anisotropy of bulk iron suggests superparamagnetic behavior in this size range, ferromagnetically blocked particles are also found at all sizes. Spontaneous transitions from the blocked state to the superparamagnetic state are observed in single particles and suggest that the enhanced magnetic energy barriers in the ferromagnetic particles are due to metastable, structurally excited states with unexpected life times

Direct Observation of Magnetic Metastability in Individual Iron Nanoparticles

X-ray photoemission electron microscopy combined with x-ray magnetic circular dichroism is used to study the magnetic properties of individual iron nanoparticles with sizes ranging from 20 down to 8 nm. While the magnetocrystalline anisotropy of bulk iron suggests superparamagnetic behavior in this size range, ferromagnetically blocked particles are also found at all sizes. Spontaneous transitions from the blocked state to the superparamagnetic state are observed in single particles and suggest that the enhanced magnetic energy barriers in the ferromagnetic particles are due to metastable, structurally excited states with unexpected life times

1.84 micron emission of Tm3+ sensitized by Yb3+ ions in monoclinic KGd(WO4)2 single crystals

By exciting at 940 nm, we have characterized the 1.84 m near infrared emission of trivalent thulium ions in Yb3+, Tm3+:KGd WO4 2 single crystals as a function of the dopant concentration and temperature, from 10 K to room temperature. An overall 3H6 Stark splitting of 470 cm−1 for the Tm3+ ions in the Yb3+, Tm3+:KGd WO4 2 was obtained. We also studied the blue emission at 476 nm Tm3+ and the near infrared emissions at 1.48 m Tm3+ and 1 m Yb3+ as a function of the dopant concentration. Experimental decay times of the 1G4, 3H4, and 3F4 Tm3+ and 2F5/2 Yb3+ excited states have been measured as a function of Yb3+ and Tm3+ ion concentrations. For the 3F4 →3H6 transition of Tm3+ ions, we used the reciprocity method to calculate the maximum emission cross section of 3.07 10−20 cm2 at 1.84 m for the polarization parallel to the Nm principal optical direction.