Hydroquinone-bridged dinuclear Cu(II) complexes and single-crystalline Cu(II) coordination polymers

Cationic dinuclear Cu(II) complexes 3 and 4 have been prepared using the novel hydroquinone-based imine chelators 2,5-((i)Pr(2)NCH(2)CH(2)N[double bond, length as m-dash]CH)(2)-1,4-(OH)(2)-C(6)H(2) (1) and 2,5-(pyCH(2)CH(2)N[double bond, length as m-dash]CH)(2)-1,4-(OH)(2)-C(6)H(2) (2), respectively (py = 2-pyridyl). X-Ray quality crystals of both complexes were grown from their DMF solutions. The sterically more encumbered compound crystallizes in the form of discrete dinuclear entities with Cu(II) centres in a distorted square-planar ligand environment (one coordination site is occupied by a DMF molecule). The pyridyl derivative 4 features dinuclear hydroquinone-bridged subunits similar to 3. However, the Cu(II) ions are now six-coordinate with two DMF molecules at an axial and an equatorial position of a Jahn-Teller-distorted octahedron. Moreover, the dinuclear subunits are no longer isolated but linked with each other via bridging hydroquinone oxygen atoms which occupy the second apical position of each octahedron. The structure suggests that the magnetic properties of the resulting coordination polymer of 4 could be described by a model valid for dimerized spin chains. As a result of this analysis the antiferromagnetic coupling constants J(1)/k(B) = 9.9 K (intradimer) and J(2)/k(B) = 0.9 K (interdimer) are obtained. Both in 3 and in 4, the hydroquinone --> semiquinone transition of the central bridging unit (E degrees ' = + 0.57 V, 3; E degrees ' = + 0.51 V, 4; DMF; vs. SCE) displays features of chemical reversibility. In the case of , reduction of Cu(II) centres requires a peak potential of E(p) = - 0.42 V.     

Development of a convenient new synthetic route to [3]ferrocenophanones

[3]Ferrocenophanone rac-8 was prepared by several non-Friedel-Crafts pathways starting from a Mannich-type coupling of 1,1'-diacetylferrocene followed by catalytic hydrogenation. Hydride abstraction from the resulting alpha-dimethylamino[3]ferrocenophane rac-14 with B(C6F5)3 followed by hydrolysis gave the ketone rac-8. Several variants of the Sommelet reaction, using ethylglyoxylate, formaldehyde or hexamethylenetetramine (urotropine) as the "oxidizing" reagent gave the alpha-[3]ferrocenophanone 8 in good to excellent yield. Some variants of these reactions were also used for the preparation of the pure enantiomer (R)-8. The electrochemical behaviour of 8 has been investigated and compared with related derivatives.     

Compositional and technological features of glazed pottery from Aosta Valley (Italy): a SEM–EDS investigation

Twelve finds from archaeological excavations carried out in the Aosta region (Italy) were studied by scanning electron microscopy coupled with energy-dispersive X-ray detection (SEM–EDS). The archaeological samples were shards of glazed pottery dating from the fourth to the seventh century AD. Analysis of ceramic bodies revealed a general homogeneity in composition among the studied samples and the use of a noncalcareous clay for their manufacture; however, two shards stand out due to their high iron contents. Glazes proved to be high-lead products with more than 70% PbO in all of the samples investigated but one. For the latter, a composition poorer in lead and richer in silicon, aluminium and iron was found. SEM observation of the contact region between body and glaze suggests that the vitreous coatings were mostly obtained by applying the glazing components onto the unfired clay body; moreover, a comparison between clay and glaze compositions suggests the use of a lead compound mixed with a silica-rich material, not a lead compound by itself.     

Diffusion-weighted MRI in the characterization of cystic pancreatic lesions: usefulness of ADC values

Purpose

To evaluate the usefulness of diffusion-weighted magnetic resonance imaging (DW-MRI) in the differentiation of cystic pancreatic lesions.

Materials and Methods

Institutional review board approval was obtained, and written informed consent was taken from all enrolled subjects. Fifty-four patients with cystic pancreatic lesions of at least 1 cm in diameter (range:10–96 mm) at ultrasonography and/or computed tomography and 10 normal subjects underwent MRI at 1.5 T. These subjects included thirty-four patients with intraductal papillary mucinous tumors (IPMTs), 10 with pseudocysts, 5 with serous cystoadenoma and 5 with mucinous cystoadenoma. The MR protocol included axial T1w and T2w sequences and coronal MR cholangiopancreatography images. DW-MRI was performed using a breath-hold single-shot echo-planar sequence with a b gradient factor value of 500 s/mm² in the three orthogonal axes. Apparent diffusion coefficient (ADC) was calculated for cerebrospinal fluid, normal pancreatic parenchyma, and for each focal pancreatic lesion. Imaging results were correlated with endoscopic retrograde cholangiopancreatography, endoscopic ultrasound-guided fine needle aspiration, surgery and/or imaging follow-up.

Results

Mean ADC value was 4.1×10⁻³ mm²/s for cerebrospinal fluid, 1.73×10⁻³ mm²/s for normal pancreatic parenchyma, 4.09×10⁻³ mm²/s for IPMT, 3.89×10⁻³ mm²/s for mucinous cystoadenoma, 3.65×10⁻³ mm²/s for serous cystoadenoma and 2.83×10⁻³ mm²/s for pseudocyst. Mean ADC values of each of the different types of pancreatic lesions were statistically different (P<.05).

Conclusion

DW-MRI may be helpful in the differential diagnosis of cystic pancreatic lesions.     

Reversible interconversion between a supramolecular polymer and a discrete octameric species from a guanosine derivative by dynamic cation binding and release

[reaction: see text] The tunable interconversion between two highly ordered supramolecular motifs (G-quartet K(+)-templated column and G-ribbon) of a lipophilic guanosine derivative fueled by cation complexation and release in a cryptand [2.2.2] containing guanosine solution is reported. The process is controlled by the sequential addition of acid and base.     

Focal nodular hyperplasia of the liver: diffusion and perfusion MRI characteristics

Purpose

To present diffusion and perfusion magnetic resonance imaging (MRI) characteristics of focal nodular hyperplasia (FNH) of the liver.

Materials and Methods

Thirty-five patients with 52 FNHs (21 were pathologically-confirmed) underwent MRI at 1.5-T device. MR diffusion [diffusion-weighted imaging (DWI)] was performed using a free-breathing single-shot, spin-echo, echo-planar sequence with b gradient factor value of 500 s/mm². MR perfusion [perfusion-weighted imaging (PWI)] consisted of a 3D free-breathing LAVA sequence repeated up to 5 minutes after injection of 7 mL Gd-BOPTA (MultiHance, Bracco, Italy) and 20 mL saline flush at a flow rate of 4 mL/s. Apparent diffusion coefficient (ADC) and time-signal intensity curve (TSIC) were obtained for both normal liver and each FNH by two reviewers in conference; maximum enhancement (ME) percentage, time to peak enhancement (TTP), and maximal slope (MS) were also calculated.

Results

On DWI mean ADC value was 1.624×10^− 3 mm²/s for normal liver and 1.629×10^− 3 mm²/s for FNH. ADC value for each FNH and the normal liver was not statistically different (P= .936). On PWI, TSIC-Type 1 (quick and marked enhancement and quick decay followed by slowly decaying) was observed in all 52 FNHs, and TSIC-Type 2 (fast enhancement followed by slowly decaying plateau) in all normal livers. The mean ME, TTP and MS values were significantly different for FNH and normal liver (P= .005).

Conclusion

FNHs of the liver showed typical diffusion and perfusion MRI characteristics in all cases. On the ADC map, we could get similar value between the FNHs and the background parenchyma. On the perfusion imaging, FNHs showed a different pattern distinguished from the background liver.     

Stabilization and error bounds for the inverse laplace transform

We present some theorems on the stabilization of the inverse Laplace transform. We assume the Laplace transform is measured at N points to within some error ?. We prove error bounds for the inverse Laplace transform in terms of ? and N, under suitable a-priori constraints. This is achieved by proving parallel stabilization results for a related Hausdorff moment problem.     

Shilnikov lemma for a nondegenerate critical manifold of a Hamiltonian system

Let M be a normally hyperbolic symplectic critical manifold of a Hamiltonian system. Suppose M consists of equilibria with real eigenvalues. We prove an analog of the Shilnikov lemma (strong version of the λ-lemma) describing the behavior of trajectories near M. Using this result, trajectories shadowing chains of homoclinic orbits to M are represented as extremals of a discrete variational problem. Then the existence of shadowing periodic orbits is proved. This paper is motivated by applications to the Poincaré’s second species solutions of the 3 body problem with 2 masses small of order µ. As µ → 0, double collisions of small bodies correspond to a symplectic critical manifold M of the regularized Hamiltonian system. Thus our results imply the existence of Poincaré’s second species (nearly collision) periodic solutions for the unrestricted 3 body problem.     

Layered solutions with multiple asymptotes for non autonomous Allen–Cahn equations in {\mathbb {R}^{3}}

We consider a class of semilinear elliptic equations of the form $$ \label{eq:abs}-\Delta u(x,y,z)+a(x)W'(u(x,y,z))=0,\quad (x,y,z)\in\mathbb {R}^{3},$$ where ${a:\mathbb {R} \to \mathbb {R}}$ is a periodic, positive, even function and, in the simplest case, ${W : \mathbb {R} \to \mathbb {R}}$ is a double well even potential. Under non degeneracy conditions on the set of minimal solutions to the one dimensional heteroclinic problem $$-\ddot q(x)+a(x)W^{\prime}(q(x))=0,\ x\in\mathbb {R},\quad q(x)\to\pm1\,{\rm as}\, x\to \pm\infty,$$ we show, via variational methods the existence of infinitely many geometrically distinct solutions u of (0.1) verifying u(x, y, z) → ± 1 as x → ± ∞ uniformly with respect to ${(y, z) \in \mathbb {R}^{2}}$ and such that ${\partial_{y}u \not \equiv0, \partial_{z}u \not\equiv 0}$ in ${\mathbb {R}^{3}}$ .     

Vibrationally resolved K-shell photoionization cross sections of methane

We use an extension of the static-exchange density functional theory (DFT) method, previously reported in [E. Plésiat et al., Phys. Rev. A 2, 023409 (2012), E. Plésiat, P. Decleva, F. Martín, Phys. Chem. Chem. Phys. 31, 10853 (2012)], to evaluate vibrationally resolved (total and angular) K-shell photoelectron cross sections of methane. The calculated cross sections are in very good agreement with the existing experimental measurements at low photoelectron energies. We show that, in contrast with the rich interference patterns previously observed in molecular frame C(1s) photoelectron angular distributions of methane at both low and high photoelectron energy, no interference effects are observed in the calculated β parameters, even at high photon energies.