A delayed class of BOLD waveforms associated with spreading depression in the feline cerebral cortex can be detected and characterised using independent component analysis (ICA)

An application of independent component analysis to blood oxygenation level- dependent MRI (BOLD-MRI) results was used to detect cerebrovascular changes that followed the initiation of cortical spreading depression (CSD) in feline brain. The cortical images were obtained from a horizontal plane at 28 s intervals before, and for 1.4-1.75 h after, KCl dissolved in agar (KCl/agar) had been directly applied to the left suprasylvian gyrus of 13 anesthetized cats for 10 min. It successfully resolved, for the first time, a novel class of prolonged, and delayed, biphasic BOLD waveforms. These were larger in amplitude ( approximately 20%), longer lasting and more delayed in onset (13-33 min) than the brief propagating (90 s) BOLD increase ( approximately 4%) already known to be associated with CSD on earlier occasions. Furthermore, such changes occurred in localized regions on the hemisphere ipsilateral to the site of stimulus application in 4 out of 5 control subjects rather than themselves generating propagating waves. Finally, the biphasic waveforms were consistently abolished in the 4 experimental animals studied following the i.v. administration of sumatriptan (0.3 mg kg(-1)), an antimigraine 5-HT(1B/1D) agonist, 15 min before the application of the transient stimulus. They were abolished in 2 out of 4 animals following the intraperitoneal (i.p.) administration of SB-220453 (tonabersat: 10 mg kg(-1), 90 min before stimulus application), a novel anticonvulsant that has recently been reported to inhibit CSD. ICA has thus been successful in detecting a novel localized, as opposed to propagating, signal of potential physiological significance hidden in complex BOLD- MRI data, whose sensitivity to sumatriptan may relate it to the cerebrovascular changes reported in the headache phase of migraine.     

Crossover scaling of wavelength selection in directional solidification of binary alloys

We simulate cellular and dendritic growth in directional solidification in dilute binary alloys using a phase-field model solved with adaptive-mesh refinement. The spacing of primary branches is examined for a wide range of thermal gradients and alloy compositions and is found to undergo a maximum as a function of pulling velocity, in agreement with experimental observations. We demonstrate that wavelength selection is unambiguously described by a nontrivial crossover scaling function from the emergence of cellular growth to the onset of dendritic fingers. This result is further validated using published experimental data, which obeys the same scaling function.     

A structural and theoretical investigation of equatorial cis and trans uranyl phosphinimine and uranyl phosphine oxide complexes UO2Cl2(Cy3PNH)2 and UO2Cl2(Cy3PO)2

Phosphinimine ligands (Cy3PNH) readily react with UO2Cl2(THF)3 (THF=tetrahydrofuran) to give UO2Cl2(Cy3PNH)2, which contains strong U-N interactions and exists as cis and trans isomers in the solid and solution state. Solution NMR experiments and computational analysis both support the trans form as the major isomer in solution, although the cis isomer becomes more stabilized with an increase in the dielectric constant of the solvent. Mayer bond orders, energy decomposition analysis, and examination of the molecular orbitals and total electron densities support a more covalent bonding interaction in the U-NHPCy3 bond compared with the analogous bond of the related U-OPCy3 compounds.     

Trivalent [(C5Me5)2(THF)Ln]2(mu-eta2:eta2-N2) complexes as reducing agents including the reductive homologation of CO to a ketene carboxylate, (mu-eta4-O2C-C=C=O)2-

The [Z(2)Ln(THF)](2)(mu-eta(2)():eta(2)()-N(2)) complexes (Z = monoanionic ligand) generated by reduction of dinitrogen with trivalent lanthanide salts and alkali metals are strong reductants in their own right and provide another option in reductive lanthanide chemistry. Hence, lanthanide-based reduction chemistry can be effected in a diamagnetic trivalent system using the dinitrogen reduction product, [(C(5)Me(5))(2)(THF)La](2)(mu-eta(2)():eta(2)()-N(2)), 1, readily obtained from [(C(5)Me(5))(2)La][BPh(4)], KC(8), and N(2). Complex 1 reduces phenazine, cyclooctatetraene, anthracene, and azobenzene to form [(C(5)Me(5))(2)La](2)[mu-eta(3):eta(3)-(C(12)H(8)N(2))], 2, (C(5)Me(5))La(C(8)H(8)), 3, [(C(5)Me(5))(2)La](2)[mu-eta(3):eta(3)-(C(14)H(10))], 4, and [(C(5)Me(5))La(mu-eta(2)-(PhNNPh)(THF)](2), 5, respectively. Neither stilbene nor naphthalene are reduced by 1, but 1 reduces CO to make the ketene carboxylate complex {[(C(5)Me(5))(2)La](2)[mu-eta(4)-O(2)C-C=C=O](THF)}(2), 6, that contains CO-derived carbon atoms completely free of oxygen.     

T-REX

The potential barrier impeding the spontaneous emission of protons in the proton radioactive nuclei is calculated as the sum of nuclear, Coulomb and centrifugal contributions. The nuclear part of the proton-nucleus interaction potential is obtained in the energy density formalism using the Skyrme effective interaction that results into a simple algebraic expression. The half-lives of the proton emitters are calculated for the different Skyrme sets within the improved WKB framework. The results are found to be in reasonable agreement with the earlier results obtained for more complicated calculations involving finite-range interactions.     

A covariance fitting approach for correlated acoustic source mapping

Microphone arrays are commonly used for noise source localization and power estimation in aeroacoustic measurements. The delay-and-sum (DAS) beamformer, which is the most widely used beamforming algorithm in practice, suffers from low resolution and high sidelobe level problems. Therefore, deconvolution approaches, such as the deconvolution approach for the mapping of acoustic sources (DAMAS), are often used for extracting the actual source powers from the contaminated DAS results. However, most deconvolution approaches assume that the sources are uncorrelated. Although deconvolution algorithms that can deal with correlated sources, such as DAMAS for correlated sources, do exist, these algorithms are computationally impractical even for small scanning grid sizes. This paper presents a covariance fitting approach for the mapping of acoustic correlated sources (MACS), which can work with uncorrelated, partially correlated or even coherent sources with a reasonably low computational complexity. MACS minimizes a quadratic cost function in a cyclic manner by making use of convex optimization and sparsity, and is guaranteed to converge at least locally. Simulations and experimental data acquired at the University of Florida Aeroacoustic Flow Facility with a 63-element logarithmic spiral microphone array in the absence of flow are used to demonstrate the performance of MACS.     

Probing the reactivity and electronic structure of a uranium(V) terminal oxo complex

Treatment of the U(III)-ylide adduct U(CH(2)PPh(3))(NR(2))(3) (1, R = SiMe(3)) with TEMPO generates the U(V) oxo metallacycle [Ph(3)PCH(3)][U(O)(CH(2)SiMe(2)NSiMe(3))(NR(2))(2)] (2) via O-atom transfer, in good yield. Oxidation of 2 with 0.85 equiv of AgOTf affords the neutral U(VI) species U(O)(CH(2)SiMe(2)NSiMe(3))(NR(2))(2) (3). The electronic structures of 2 and 3 are investigated by DFT analysis. Additionally, the nucleophilicity of the oxo ligands in 2 and 3 toward Me(3)SiI is explored.     

Multiple positive solutions for nonlinear periodic problems

We consider a nonlinear periodic equation driven by the scalar p-Laplacian and with a Caratheodory asymptotically (p−1)-linear nonlinearity. Using variational methods coupled with suitable truncation techniques, we show that the problem has at least two positive solutions. For the semilinear case (p=2), using Morse theory we show that the problem has three distinct positive solutions.     

Isoflavonoid Profiling and Estrogen-Like Activity of Four Genista Species from the Greek Flora

As part of our ongoing research on phytoestrogens, we investigated the phytochemical profile and estrogen-like activities of eight extracts from the aerial parts of four Genista species of Greek flora using estrogen-responsive cell lines. Ethyl acetate and methanolic extracts of G. acanthoclada, G. depressa, G. hassertiana, and G. millii were obtained with accelerated solvent extraction and their phytochemical profiles were compared using ultra-high-performance liquid chromatography-high-resolution mass spectrometry (uHPLC-HRMS). Fourteen isoflavonoids, previously isolated from G. halacsyi, were used as reference standards for their identification in the extracts. Thirteen isoflavonoids were detected in both extracts of G. acanthoclada and G. hassertiana, while fewer and far fewer were detected in G. millii and G. depressa, respectively. The ethyl acetate extracts of G. hassertiana and G. acanthoclada displayed 2.45- and 1.79-fold higher, respectively, estrogen-like agonist activity in Ishikawa cells compared to MCF-7 cells at pharmacologically relevant concentrations. Both these extracts, but not that of G. depressa, contained mono- and di-O-β-d-glucosides of genistein as well as the aglycone, all three of which are known to display full estrogen-like activity at lower-than-micromolar concentrations. The possibility of using preparations rich in G. hassertiana and/or G. acanthoclada extracts as a potentially safer substitute for low-dose vaginal estrogen for menopausal symptoms is discussed.     

Quantum chemical studies of the hydration of Sr2+ in vacuum and aqueous solution

The geometric structures of gas-phase Sr(2+) hydrates are calculated quantum chemically by using hybrid (B3LYP) and meta-GGA (TPSS) density functional theory, and a range of thermodynamic data (including sequential bond enthalpies, entropies and free energies for the reactions Sr(2+)(H(2)O)(n-1)+H(2)O→Sr(2+)(H(2)O)(n)) are shown to be in excellent agreement with experiment. When the number of coordinating water molecules exceeds six, such that water begins to occupy the second solvation shell, it is found that detailed analysis based on both geometrical and conformational entropy is required in order to confidently identify the experimentally observed structures. The significant increase in coordination number observed experimentally between the gas- and aqueous-phase species is successfully reproduced, as is the first solvation shell geometry. Inaccurate second shell geometries imply that larger model systems may be required to achieve agreement with experiment. Candidate species for on-going computational studies of the interaction of hydrated Sr(2+) with brucite surfaces have been identified.