Spin-canted antiferromagnetic phase transitions in alternating phenoxo- and carboxylato-bridged Mn(III)-salen complexes

Three new MnIII complexes, {[Mn-2(salen)(2)(OCn)](ClO4)}(n) (1), {[Mn-2(salen)(2)(OPh)](ClO4)}(n) (2) and {[Mn-2(salen)(2)(OBz)](ClO4)}(2) (3) (where salen = N,N'-bis(salicylidene)-1,2-diaminoethane dianion, OCn = cinnamate, OPh = phenylacetate and OBz = benzoate), have been synthesized and characterized structurally and magnetically. The crystal structures reveal that all three structures contain syn-anti carboxylatebridged dimeric [Mn-2(salen)(2)(OOCR)](+) cations (OOCR = bridging carboxylate) that are joined together by weak Mn center dot center dot center dot O(phenoxo) interactions to form infinite alternating chain structures in 1 and 2, but the relatively long Mn center dot center dot center dot O(phenoxo) distance [3.621(2)angstrom] in 3 restricts this structure to tetranuclear units. Magnetic studies showed that 1 and 2 exhibited magnetic long-range order at T-N = 4.0 and 4.6 K (T-N = Neel transition temperature), respectively, to give spin-canted antiferromagnetic structures. Antiferromagnetic coupling was also observed in 3 but no peaks were recorded in the field-cooled magnetization (FCM) or zero-field-cooled magnetization (ZFCM) data, indicating that 3 remained paramagnetic down to 2 K. This dominant antiferromagnetic coupling is attributed to the carboxylate bridges. The ferromagnetic coupling expected due to the Mn-O(phenoxo)center dot center dot center dot Mn bridge plays an auxiliary role in the magnetic chain, but is an essential component of the bulk magnetic properties of the material.

Modulation of visually evoked cortical fMRI responses by phase of ongoing occipital alpha oscillations

Using simultaneous electroencephalography as a measure of ongoing activity and functional magnetic resonance imaging (fMRI) as a measure of the stimulus-driven neural response, we examined whether the amplitude and phase of occipital alpha oscillations at the onset of a brief visual stimulus affects the amplitude of the visually evoked fMRI response. When accounting for intrinsic coupling of alpha amplitude and occipital fMRI signal by modeling and subtracting pseudo-trials, no significant effect of prestimulus alpha amplitude on the evoked fMRI response could be demonstrated. Regarding the effect of alpha phase, we found that stimuli arriving at the peak of the alpha cycle yielded a lower blood oxygenation level-dependent (BOLD) fMRI response in early visual cortex (V1/V2) than stimuli presented at the trough of the cycle. Our results therefore show that phase of occipital alpha oscillations impacts the overall strength of a visually evoked response, as indexed by the BOLD signal. This observation complements existing evidence that alpha oscillations reflect periodic variations in cortical excitability and suggests that the phase of oscillations in postsynaptic potentials can serve as a mechanism of gain control for incoming neural activity. Finally, our findings provide a putative neural basis for observations of alpha phase dependence of visual perceptual performance.

Northern winter climate change: assessment of uncertainty in CMIP5 projections related to stratosphere–troposphere coupling

Future changes in the stratospheric circulation could have an important impact on Northern winter tropospheric climate change, given that sea level pressure (SLP) responds not only to tropospheric circulation variations but also to vertically coherent variations in troposphere-stratosphere circulation. Here we assess Northern winter stratospheric change and its potential to influence surface climate change in the Coupled Model Intercomparison Project – phase 5 (CMIP5) multi-model ensemble. In the stratosphere at high latitudes, an easterly change in zonally averaged zonal wind is found for the majority of the CMIP5 models, under the Representative Concentration Pathway 8.5 scenario. Comparable results are also found in the 1% CO2 increase per year projections, indicating that the stratospheric easterly change is common feature in future climate projections. This stratospheric wind change, however, shows a significant spread among the models. By using linear regression, we quantify the impact of tropical upper troposphere warming, polar amplification and the stratospheric wind change on SLP. We find that the inter-model spread in stratospheric wind change contributes substantially to the inter-model spread in Arctic SLP change. The role of the stratosphere in determining part of the spread in SLP change is supported by the fact that the SLP change lags the stratospheric zonally averaged wind change. Taken together, these findings provide further support for the importance of simulating the coupling between the stratosphere and the troposphere, to narrow the uncertainty in the future projection of tropospheric circulation changes.

Clustering and diffusion in a symplectic map lattice with non-local coupling

We study a symplectic chain with a non-local form of coupling by means of a standard map lattice where the interaction strength decreases with the lattice distance as a power-law, in Such a way that one can pass continuously from a local (nearest-neighbor) to a global (mean-field) type of coupling. We investigate the formation of map clusters, or spatially coherent structures generated by the system dynamics. Such clusters are found to be related to stickiness of chaotic phase-space trajectories near periodic island remnants, and also to the behavior of the diffusion coefficient. An approximate two-dimensional map is derived to explain some of the features of this connection. (C) 2008 Elsevier Ltd. All rights reserved.

Ab initio calculation of the BCC Fe-Al-Mo (Iron-Aluminum-Molybdenum) phase diagram: Implications for the nature of the tau(2) phase

The metastable phase diagram of the BCC-based ordering equilibria in the Fe-Al-Mo system has been calculated via a truncated cluster expansion, through the combination of Full-Potential-Linear augmented Plane Wave (FP-LAPW) electronic structure calculations and of Cluster Variation Method (CVM) thermodynamic calculations in the irregular tetrahedron approximation. Four isothermal sections at 1750 K, 2000 K, 2250 K and 2500 K are calculated and correlated with recently published experimental data on the system. The results confirm that the critical temperature for the order-disorder equilibrium between Fe(3)Al-D0(3) and FeAl-B2 is increased by Mo additions, while the critical temperature for the FeAl-B2/A2 equilibrium is kept approximately invariant with increasing Mo contents. The stabilization of the Al-rich A2 phase in equilibrium with overstoichiometric B2-(Fe,Mo)Al is also consistent with the attribution of the A2 structure to the tau(2) phase, stable at high temperatures in overstoichiometric B2-FeAl. (C) 2009 Elsevier Ltd. All rights reserved.

Preparation of recoverable Ru catalysts for liquid-phase oxidation and hydrogenation reactions

We here report the synthesis, characterization and catalytic performance of new supported Ru(III) and Ru(0) catalysts. In contrast to most supported catalysts, these new developed catalysts for oxidation and hydrogenation reactions were prepared using nearly the same synthetic strategy, and are easily recovered by magnetic separation from liquid phase reactions. The catalysts were found to be active in both forms, Ru(III) and Ru(0), for selective oxidation of alcohols and hydrogenation of olefins, respectively. The catalysts operate under mild conditions to activate molecular oxygen or molecular hydrogen to perform clean conversion of selected substrates. Aryl and alkyl alcohols were converted to aldehydes under mild conditions, with negligible metal leaching. If the metal is properly reduced, Ru(0) nanoparticles immobilized on the magnetic support surface are obtained, and the catalyst becomes active for hydrogenation reactions. (c) 2009 Elsevier B.V. All rights reserved.

Spectroscopic evidence of extended states in quantized Hall phase of weakly coupled GaAs/AlGaAs multi-layers

The influence of the interlayer coupling on formation of the quantized Hall conductor phase at the filling factor v = 2 was studied in the multi-layer GaAs/AlGaAs heterostructures. The disorder broadened Gaussian photoluminescence line due to the localized electrons was found in the quantized Hall phase of the isolated multi-quantum well structure. On the other hand, the quantized Hall phase of the weakly coupled multi-layers emitted an unexpected asymmetrical line similar to that one observed in the metallic electron systems. We demonstrated that the observed asymmetry is caused by a partial population of the extended electron states formed in the quantized Hall conductor phase due to the interlayer percolation. A sharp decrease of the single-particle scattering time associated with these extended states was observed at the filling factor v = 2. (c) 2007 Elsevier B.V. All rights reserved.

Peat as a natural solid-phase for copper preconcentration and determination in a multicommuted flow system coupled to flame atomic absorption spectrometry

The physical and chemical characteristics of peat were assessed through measurement of pH, percentage of organic matter, cationic exchange capacity (CEC), elemental analysis, infrared spectroscopy and quantitative analysis of metals by ICP OES. Despite the material showed to be very acid in view of the percentage of organic matter, its CEC was significant, showing potential for retention of metal ions. This characteristic was exploited by coupling a peat mini-column to a flow system based on the multicommutation approach for the in-line copper concentration prior to flame atomic absorption spectrometric determination. Cu(II) ions were adsorbed at pH 4.5 and eluted with 0.50 mol L(-1) HNO(3). The influence of chemical and hydrodynamic parameters, such as sample pH, buffer concentration, eluent type and concentration, sample flow-rate and preconcentration time were investigated. Under the optimized conditions, a linear response was observed between 16 and 100 mu g L(-1), with a detection limit estimated as 3 mu g L(-1) at the 99.7% confidence level and an enrichment factor of 16. The relative standard deviation was estimated as 3.3% (n = 20). The mini-column was used for at least 100 sampling cycles without significant variation in the analytical response. Recoveries from copper spiked to lake water or groundwater as well as concentrates used in hemodialysis were in the 97.3-111 % range. The results obtained for copper determination in these samples agreed with those achieved by graphite furnace atomic absorption spectrometry (GFAAS) at the 95% confidence level. (C) 2009 Elsevier B.V. All rights reserved.

Microwave-assisted solid-phase peptide synthesis at 60 degrees C: alternative conditions with low enantiomerization

Several conditions have been used in the coupling reaction of stepwise SPPS at elevated temperature (SPPS-ET), but we have elected the following as our first choice: 2.5-fold molar excess of 0.04-0.08 M Boc or Fmoc-amino acid derivative, equimolar amount of DIC/HOBt (1:1)or TBTU/DIPEA(1:3), 25% DMSO/toluene, 60 degrees C, conventional heating. In this study, aimed to further examine enantiomerization under such condition and study the applicability of our protocols to microwave-SPPS, peptides containing L-Ser, L-His, L-Cys and/or L-Met were manually synthesized traditionally, at 60 degrees C using conventional heating and at 60 degrees C using microwave heating. Detailed assessment of all crude peptides (in their intact and/or fully hydrolyzed forms) revealed that, except for the microwave-assisted coupling of L-Cys, all other reactions occurred with low levels of amino acid enantiomerization (<2%). Therefore, herein we (i) provide new evidences that our protocols for SPPS at 60 degrees C using conventional heating are suitable for routine use, (ii) demonstrate their appropriateness for microwave-assisted SPPS by Boc and Fmoc chemistries, (iii) disclose advantages and limitations of the three synthetic approaches employed. Thus, this study complements our past research on SPPS-ET and suggests alternative conditions for microwave-assisted SPPS. Copyright (C) 2009 European Peptide Society and John Wiley & Sons, Ltd.

Evidence for diffusional coupling in electrochemical thin layers: implications for surface coverage calibration via electrochemical infrared spectroscopy

The time dependence of the concentration of CO2 in an electrochemical thin layer cavity is studied with Fourier transform infrared spectroscopy (FTIR) in order to evaluate the extent to which the thin layer cavity is diffusionally decoupled from the surrounding bulk electrolyte. For the model system of CO on Pt(111) in 0.1 M HClO4, it is found that the concentration of CO2, formed by electro-oxidation of CO, equilibrates rapidly with the surrounding bulk electrolyte. This rapid equilibration indicates that there is diffusion out of the thin layer, even on the short time scales of typical infrared experiments (1-3 min). However, since the measured CO2 absorbance intensity as a function of time is reproducible to within 10%, a new time-dependent method for surface coverage calibration using solution-phase species is proposed.

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.

Ketamine alters oscillatory coupling in the hoppocampus

Recent studies show that higher order oscillatory interactions such as cross-frequency coupling are important for brain functions that are impaired in schizophrenia, including perception, attention and memory. Here we investigated the dynamics of oscillatory coupling in the hippocampus of awake rats upon NMDA receptor blockade by ketamine, a pharmacological model of schizophrenia. Ketamine (25, 50 and 75 mg/kg i.p.) increased gamma and high-frequency oscillations (HFO) in all depths of the CA1-dentate axis, while theta power changes depended on anatomical location and were independent of a transient increase of delta oscillations. Phase coherence of gamma and HFO increased across hippocampal layers. Phase-amplitude coupling between theta and fast oscillations was markedly altered in a dose-dependent manner: ketamine increased hippocampal theta-HFO coupling at all doses, while theta-gamma coupling increased at the lowest dose and was disrupted at the highest dose. Our results demonstrate that ketamine alters network interactions that underlie cognitively relevant theta-gamma coupling.

Ps-He scattering using the three-state positronium close-coupling approximation

A three-state target elastic positronium close-coupling approximation (CCA) is employed to investigate Ps-He scattering in the energy range 0-200 eV with and without electron exchange. Low-lying phase shifts below the first excitation threshold and the total integrated cross sections using both the models are reported. Estimation of integrated excitation cross sections for Ps(1s --> 2s) and Ps(1s --> 2p) using CCA are presented for the first time. The present total cross sections are in good agreement with the measured data in the incident Ps energy range 20-30 eV.

Rho-nucleon tensor coupling and charge-exchange resonances

The Gamow-Teller resonance in Pb-208 is discussed in the context of a self-consistent RPA, based on the relativistic mean field theory. We inquire on the possibility of substituting the phenomenological Landau-Migdal force by a microscopic nucleon-nucleon interaction, generated from the rho-nucleon tensor coupling. The effect of this coupling turns out to be very small when the short range correlations are not taken into account, but too large when these correlations are simulated by the simple extraction of the contact terms from the resulting nucleon-nucleon interaction. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Miscibility in a degenerate fermionic mixture induced by linear coupling

We consider a one-dimensional mean-field-hydrodynamic model of a two-component degenerate Fermi gas in an external trap, each component representing a spin state of the same atom. We demonstrate that the interconversion between them (linear coupling), imposed by a resonant electromagnetic wave, transforms the immiscible binary gas into a miscible state, if the coupling constant, kappa, exceeds a critical value, kappa(cr). The effect is predicted in a variational approximation, and confirmed by numerical solutions. Unlike the recently studied model of a binary Bose-Einsten condensate with the linear coupling, the components in the immiscible phase of the binary fermion mixture never fill two separated domains with a wall between them, but rather form antilocked (pi-phase-shifted) density waves. Another difference from the bosonic mixture is spontaneous breaking of symmetry between the two components in terms of the numbers of atoms in them, N(1) and N(2). The latter effect is characterized by the parameter nu equivalent to(N(1)-N(2))/(N(1)+N(2)) (only N(1)+N(2) is a conserved quantity), the onset of miscibility at kappa >=kappa(cr) meaning a transition to nu equivalent to 0. At kappa coupling, and the developing spatial structure resembles the known Larkin-Ovchinnikov-Fulde-Ferrell states in the Fermi mixture. Dynamical states, when kappa is suddenly switched from zero to a value exceeding kappa(cr), are considered too. In the latter case, the system features oscillatory relaxation to the mixed state.