Synthesis, spectroscopic characterization and X-ray structures of five-coordinate diorganotin(IV) complexes containing 5-hydroxypyrazoline derivatives as ligands

Four new diorganotin(IV) complexes have been prepared from R(2)SnCl(2) (R = Me, Ph) with the ligands 5-hydroxy-3-metyl-5-phenyl-1-(S-benzildithiocarbazate)-pyrazoline (H(2)L(1)) and 5-hydroxy-3-methyl-5-phenyl-1-(2-thiophenecarboxylic)-pyrazoline (H(2)L(2)). The complexes were characterized by elemental analysis, IR. (1)H (13)C, (119)Sn NMR and Mossbauer spectroscopes The complexes [Me(2)SnL(1)], [Ph(2)SnL(1)] and [Me(2)SnL(2)] were also studied by single crystal X-ray diffraction and the results showed that the Sn(IV) central atom of the complexes adopts a distorted trigonal bipyramidal (TBP) geometry with the N atom of the ONX-tridentate (X = O and S) ligand and two organic groups occupying equatorial sites. The C-Sn-C angles for [Me(2)Sn(L(1))] and [Ph(2)Sn(L(1))] were calculated using a correlation between (119)Sn Mossbauer and X-ray crystallographic data based on the point-charge model Theoretical calculations were performed with the B3LYP density functional employing 3-21G(*) and DZVP all electron basis sets showing good agreement with experimental findings General and Sn(IV) specific IR harmonic frequency scale factors for both basis sets were obtained from comparison with selected experimental frequencies (C) 2010 Elsevier B V All rights reserved

Light-Induced Oxidation of Unsaturated Lipids as Sensitized by Flavins

Triplet-excited riboflavin ((3)RF*) was found by laser flash photolysis to be quenched by polyunsaturated fatty acid methyl esters in tert-butanol/water (7:3, v/v) in a second-order reaction with k similar to 3.0 x 10(5) L mol(-1) s(-1) at 25 degrees C for methyl linoleate and 3.1 x 10(6) L mol(-1) s(-1), with Delta H double dagger = 22.6 kJ mol(-1) and Delta S double dagger = -62.3 J K(-1) mol(-1), for methyl linolenate in acetonitrile/water (8:2, v/v). For methyl oleate, k was <10(4) L mol(-1) s(-1). For comparison, beta-casein was found to have a rate constant k similar to 4.9 x 10(8) L mol(-1) s(-1). Singlet-excited flavin was not quenched by the esters as evidenced by insensitivity of steady-state fluorescence to their presence. Density functional theory (DFT) calculations showed that electron transfer from unsaturated fatty acid esters to triplet-excited flavins is endergonic, while a formal hydrogen atom transfer is exergonic (Delta G(HAT)degrees = -114.3, -151.2, and -151.2 kJ mol(-1) for oleate, linoleate, and linolenate, respectively, in acetonitrile). The reaction is driven by acidity of the lipid cation radical for which a pK(a) similar to -0.12 was estimated by DFT calculations. Absence of electrochemical activity in acetonitrile during cyclic voltammetry up to 2.0 V versus NHE confirmed that Delta G(ET)degrees > 0 for electron transfer. Interaction of methyl esters with (3)RF* is considered as initiation of the radical chain, which is subsequently propagated by combination reactions with residual oxygen. In this respect, carbon-centered and alkoxyl radicals were detected using the spin trapping technique in combination with electron paramagnetic resonance spectroscopy. Moreover, quenching of 3RF* yields, directly or indirectly, radical species which are capable of initiating oxidation in unsaturated fatty acid methyl esters. Still, deactivation of triplet-excited flavins by lipid derivatives was slower than by proteins (factor up to 10(4)), which react preferentially by electron transfer. Depending on the reaction environment in biological systems (including food), protein radicals are expected to interfere in the mechanism of light-induced lipid oxidation.

A quantum chemical study on a set of non-imidazole H(3) antihistamine molecules

Molecular orbital calculations were carried out on a set of 28 non-imidazole H(3) antihistamine compounds using the Hartree-Fock method in order to investigate the possible relationships between electronic structural properties and binding affinity for H3 receptors (pK(i)). It was observed that the frontier effective-for-reaction molecular orbital (FERMO) energies were better correlated with pK(i) values than highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy values. Exploratory data analysis through hierarchical cluster (HCA) and principal component analysis (PCA) showed a separation of the compounds in two sets, one grouping the molecules with high pK(i) values, the other gathering low pK(i) value compounds. This separation was obtained with the use of the following descriptors: FERMO energies (epsilon(FERMO)), charges derived from the electrostatic potential on the nitrogen atom (N(1)), electronic density indexes for FERMO on the N(1) atom (Sigma((FERMO))c(i)(2)). and electrophilicity (omega`). These electronic descriptors were used to construct a quantitative structure-activity relationship (QSAR) model through the partial least-squares (PLS) method with three principal components. This model generated Q(2) = 0.88 and R(2) = 0.927 values obtained from a training set and external validation of 23 and 5 molecules, respectively. After the analysis of the PLS regression equation and the values for the selected electronic descriptors, it is suggested that high values of FERMO energies and of Sigma((FERMO))c(i)(2), together with low values of electrophilicity and pronounced negative charges on N(1) appear as desirable properties for the conception of new molecules which might have high binding affinity. 2010 Elsevier Inc. All rights reserved.

Photodegradation of Folate Sensitized by Riboflavin

Folate is shown to react with singlet-excited state of riboflavin in a diffusion controlled reaction and with triplet-excited state of riboflavin in a somewhat slower reaction with (3)k(q) = 4.8 x 10(8) L mol(-1) s(-1) in aqueous phosphate buffer at pH 7.4, ionic strength of 0.2 mol L(-1), and 25 degrees C. Singlet quenching is assigned as photo-induced reductive electron transfer from ground state folate to singlet-excited riboflavin, while triplet quenching is assigned as one-electron transfer rather than hydrogen atom transfer from folate to triplet-excited riboflavin, as the reaction quantum yield, phi = 0.32, is hardly influenced by solvent change from water to deuterium oxide, phi = 0.37. Cyclic voltammetry showed an irreversible two-electron anodic process for folate, E = 1.14 V versus NHE at a scan-rate of 50 mV s(-1), which appears to be kinetically controlled by the heterogeneous electron transfer from the substrates to the electrode. Main products of folate photooxidation sensitized by riboflavin were pterin-6-carboxylic acid and p-aminobenzoyl-L-glutamic acid as shown by liquid chromatographic ion-trap mass spectrometry (LC-IT-MS).

Mixed-Ligand Complexes of Technetium and Rhenium with Tridentate Benzamidines and Bidentate Benzoylthioureas

Mixed-ligand complexes of technetium(V) or rhenium(V) containing tridentate N-[(dialkylamino)(thiocarbonyl)]benzamidine (H(2)L(1)) and bidentate N,N-dialkyl-N`-benzoylthiourea (HL(2)) ligands were formed in high yields when (NBu(4))[MOCl(4)] (M = Tc or Re) or [ReOCl(3)(PPh(3))(2)] was treated with mixtures of the proligands. Other approaches for the synthesis of the products are reactions of [MOCl(L(1))] complexes with HL(2) or compounds of the-composition [ReOCl(2)(PPh(3))(L(2))] with H(2)L(1). The resulting air-stable [MO(L(1))(L(2))] complexes possess potential for the development of metal-based radiopharmaceuticals. [TcO(L(1))(L(2))] complexes are readily reduced by PPh3 with formation of [Tc(L(1))(L(2))(PPh(3))]. The resulting Tc(III) complexes undergo two almost-reversible oxidation steps corresponding to one-electron transfer processes. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Cationic and neutral phenylmercury(II) complexes with heterocyclic thione ligands. X-ray structures of [HgPh(dmpymtH)][BF(4)] center dot H(2)O and [{HgPh}(2)(mu-dtu)]

The neutral complex [HgPh(dmpymt)] 1 (dmpymtH = 4,6-dimethylpyrimidine-2(1H)-thione) reacts with HBF(4) to give the cationic complex [HgPh(dmpymtH)][BF(4)] 2. The X-ray molecular structure of the later revealed a [2+1] coordination sphere about the mercury(II) atom (C-Hg-S and Hg center dot center dot center dot N). In the dinuclear complex [(HgPh)(2)(mu-dtu)] 3 [dtuH(2) = 2,4(1H,3H)-pyrimidinedithione or dithiouracil] the coordination spheres are also [2+1] although dissimilar regarding the Hg center dot center dot center dot N secondary bonds. NMR spectroscopy ((1)H, (13)C and (199)Hg) studies were undertaken in solution and the results discussed in the light of the X-ray structures. (C) 2008 Elsevier B. V. All rights reserved.

Reflection of matter waves in potential structures

In this paper the behavior of matter waves in suddenly terminated potential structures is investigated numerically. It is shown that there is no difference between a fully quantum mechanical treatment and a semiclassical one with regards to energy redistribution. For the quantum case it is demonstrated that there can be substantial reflection at the termination. The neglect of backscattering by the semiclassical method brings about major differences in the case of low kinetic energies. A simple phenomenological model is shown to partially explain the observed backscattering using dynamics of reduced dimensionality.

Adiabatic propagation in potential structures

In this work the adiabatic approximation is applied to the propagation of matter waves in confined geometries like those experimentally realized in recent atom optical experiments. Adiabatic propagation along a channel is assumed not to mix the various transverse modes. Nonadiabatic corrections arise from the potential squeezing and bending. Here we investigate the effect of the former. Detailed calculations of two-dimensional propagation are carried out both exactly and in an adiabatic approximation. This offers the possibility to analyze the validity of adiabaticity criteria. A semiclassical (sc) approach, based on the sc Massey parameter is shown to be inadequate, and the diffraction due to wave effects must be included separately. This brings in the Fresnel parameter well known from optical systems. Using these two parameters, we have an adequate understanding of adiabaticity on the system analyzed. Thus quantum adiabaticity must also take cognizance of the intrinsic diffraction of matter waves.

Localization in splitting of matter waves

In this paper we present an analysis of how matter waves, guided as propagating modes in potential structures, are split under adiabatic conditions. The description is formulated in terms of localized states obtained through a unitary transformation acting on the mode functions. The mathematical framework results in coupled propagation equations that are decoupled in the asymptotic regions as well before as after the split. The resulting states have the advantage of describing propagation in situations, for instance matter-wave interferometers, where local perturbations make the transverse modes of the guiding potential unsuitable as a basis. The different regimes of validity of adiabatic propagation schemes based on localized versus delocalized basis states are also outlined. Nontrivial dynamics for superposition states propagating through split potential structures is investigated through numerical simulations. For superposition states the influence of longitudinal wave-packet extension on the localization is investigated and shown to be accurately described in quantitative terms using the adiabatic formulations presented here.

Limits to phase resolution in matter-wave interferometry

We study the quantum dynamics of a two-mode Bose-Einstein condensate in a time-dependent symmetric double-well potential using analytical and numerical methods. The effects of internal degrees of freedom on the visibility of interference fringes during a stage of ballistic expansion are investigated varying particle number, nonlinear interaction sign and strength, as well as tunneling coupling. Expressions for the phase resolution are derived and the possible enhancement due to squeezing is discussed. In particular, the role of the superfluid-Mott insulator crossover and its analog for attractive interactions is recognized.

Polarizing beam splitter for dipolar molecules

We propose a coherent beam splitter for polarized heteronuclear molecules based on a stimulated Raman adiabatic passage scheme that uses a tripod linkage of electrotranslational molecular states. We show that for strongly polarized molecules the rotational dynamics imposes significantly larger Rabi frequencies than would otherwise be expected, but within this limitation, a full transfer of the molecules to two counterpropagating ground-state wave packets is possible.

Dynamics of Bose-Einstein condensates in double-well potentials

We study the dynamics of Bose-Einstein condensates in symmetric double-well potentials following a sudden change of the potential from the Mott-insulator to the superfluid regime. We introduce a continuum approximation that maps that problem onto the wave-packet dynamics of a particle in an anharmonic effective potential. For repulsive two-body interactions the visibility of interference fringes that result from the superposition of the two condensates following a stage of ballistic expansion exhibits a collapse of coherent oscillations onto a background value whose magnitude depends on the amount of squeezing of the initial state. Strong attractive interactions are found to stabilize the relative number dynamics. We visualize the dynamics of the system in phase space using a quasiprobability distribution that allows for an intuitive interpretation of the various types of dynamics.

Coherence dynamics of two-mode condensates in asymmetric potentials

Detection of weak forces with an accuracy beyond the standard quantum limit holds promise both for fundamental research and for technological applications. Schemes involving ultracold atoms for such measurements are now considered to be prime candidates for increased sensitivity. In this paper we use a combination of analytical and numerical techniques to investigate the possible subshot-noise estimation of applied force fields through detection of coherence dynamics of Bose-condensed atoms in asymmetric double-well traps. Following a semiclassical description of the system dynamics and fringe visibility, we present numerical simulations of the full quantum dynamics that demonstrate the dynamical production of phase squeezing beyond the standard quantum limit. Nonlinear interactions are found to limit the achievable amount to a finite value determined by the external weak force.

Single-mode acceleration of matter waves in circular waveguides

Ultracold gases in ring geometries hold promise for significant improvements of gyroscopic sensitivity. Recent experiments have realized atomic and molecular storage rings with radii in the centimeter range, sizes whose practical use in inertial sensors requires velocities significantly in excess of typical recoil velocities. We use a combination of analytical and numerical techniques to study the coherent acceleration of matter waves in circular waveguides, with particular emphasis on its impact on single-mode propagation. In the simplest case we find that single-mode propagation is best maintained by the application of time-dependent acceleration force with the temporal profile of a Blackmann pulse. We also assess the impact of classical noise on the acceleration process.

Thomas-Fermi ground state of dipolar fermions in a circular storage ring

Recent developments in the field of ultracold gases has led to the production of degenerate samples of polar molecules. These have large static electric-dipole moments, which in turn causes the molecules to interact strongly. We investigate the interaction of polar particles in waveguide geometries subject to an applied polarizing field. For circular waveguides, tilting the direction of the polarizing field creates a periodic inhomogeneity of the interparticle interaction. We explore the consequences of geometry and interaction for stability of the ground state within the Thomas-Fermi model. Certain combinations of tilt angles and interaction strengths are found to preclude the existence of a stable Thomas-Fermi ground state. The system is shown to exhibit different behavior for quasi-one-dimensional and three-dimensional trapping geometries.