Two isomorphous cobalt(II) complexes: poly[[diaqua‐μ‐2,5‐dicarboxybenzene‐1,4‐dicarboxylato‐μ‐1,2‐di‐4‐pyridylethene‐cobalt(II)] 1,2‐di‐4‐pyridylethene solvate] and the 1,2‐di‐4‐pyridylethane analogue

The two isomorphous title structures, formulated as {[Co(C₁₀H₄O₈)(C₁₂H₁₀N₂)(H₂O)₂]·C₁₂H₁₀N₂}_n, (I), and {[Co(C₁₀H₄O₈)(C₁₂H₁₂N₂)(H₂O)₂]·C₁₂H₁₂N₂}_n, (II), respectively, are reported. They crystallize in the space group P with only one formula unit in the asymmetric unit, so that the organic ligands lie about inversion centres and the Co atom lies on an inversion centre. The Co atoms are octahedrally coordinated by a carboxylate O atom from 2,5‐dicarboxybenzene‐1,4‐dicarboxylate (H₂btc), one N atom from 1,2‐di‐4‐pyridylethene (L) in (I) or from 1,2‐di‐4‐pyridylethane (L) in (II), and one coordinated water molecule, plus their inversion‐related species. This particular coordination results in a two‐dimensional array, with an elemental unit in the shape of a parallelogram having the Co^II cations at the corners, linked in one direction by L bridges and in the opposite direction by H₂btc groups. The L solvent molecules act as pillars between parallel planes, linking them by strong hydrogen bonds where the H atoms lie midway between the formal donor/acceptor atoms in a `shared' mode. Comparison is made with structures presenting the same structural motif, strongly suggesting that the two‐dimensional arrangement reported here might be a very stable robust building block for molecular engineering purposes.     

Violations of lepton-flavour universality in P→?ν decays: a?model-independent analysis

We analyse the violations of lepton-flavour universality in the ratios ℬ(P→ℓ ν)/ℬ(P→ℓ ^′ ν) using a general effective theory approach, discussing various flavour-symmetry breaking patterns of physics beyond the SM. We find that in models with Minimal Lepton Flavour Violation the effects are too small to be observed in the next generations of experiments in all relevant meson systems (P=π,K,B). In a Grand Unified framework with minimal breaking of the flavour symmetry, the effects remain small in π and K decays, while large violations of lepton-flavour universality are possible in B→ℓ ν decays.     

Facile transformation of glutamic acid into proline residue inside a tripeptide backbone

In this Letter we present a simple reaction pathway which allows the conversion of the glutamic acid residue of a tripeptide into a proline residue. The reaction was performed by using Boc-Val-Glu-Phe-NH₂ as a starting material and is based on a NaH-induced intraresidue alkylation under reaction conditions analogous to that adopted during the Freidinger lactams formation.     

Efficacy of nanolime in restoration procedures of salt weathered limestone rock

Salt crystallisation process is one of the most powerful weathering agents in stone materials, especially in the coastal areas, where sea-spray transports large amount of salts on the stone surface. The consolidation of such degraded stone material represents a critical issue in the field of restoration of cultural heritage. In this paper, the nanolime consolidation behaviour in limestone degraded by salt crystallization has been assessed. For this purpose, a stone material taken from a Sicilian historical quarry and widely used in the eastern Sicilian Baroque architecture has been artificially degraded by the salt crystallization test. Then degraded samples have been treated with NanoRestore^®, a suspension of nanolime in isopropyl alcohol. To evaluate the consolidating effectiveness, the peeling test and point load test were performed. Moreover, mercury intrusion porosimetry has been executed to evaluate the variations induced by treatment, while colorimetric measurements have been aimed to assess aesthetical issues.     

Tantalum nanoparticles enhance the osteoinductivity of multiscale composites based on poly(lactide-co-glycolide) electrospun fibers embedded in a gelatin hydrogel

Bioresorbable polymeric materials have risen great interest as implants for bone tissue regeneration, since they show substantial advantages with respect to conventional metal devices, including biodegradability, flexibility, and the possibility to be easily modified to introduce specific functionalities. In the present work, an innovative nanocomposite scaffold, properly designed to show biomimetic and osteoinductive properties for potential application in bone tissue engineering, was developed. The scaffold is characterized by a multi-layer structure, completely different with respect to the so far employed polymeric implants, consisting in a poly(d,l-lactide-co-glycolide)/polyethylene glycol electrospun nanofibrous mat sandwiched between two hydrogel gelatin layers enriched with tantalum nanoparticles (NPs). The composition of the electrospun fibers, containing 10 wt% of polyethylene glycol, was selected to ensure a proper integration of the fibers in the gel phase, essential to endow the composite with flexibility and to prevent delamination between the layers. The scaffold maintained its structural integrity after six weeks of soaking in physiological solutions, albeit the gelatin phase was partially released. The combined use of gelatin, bioresorbable electrospun fibers and tantalum NPs endows the final device with biomimetic and osteoinductive properties. Indeed, results of the in vitro tests demonstrate that the obtained scaffolds clearly represent a favorable milieu for normal human bone-marrow derived mesenchymal stem cells viability and osteoblastic differentiation; moreover, inclusion of tantalum NPs in the scaffold improves cell performance with particular regard to early and late markers of osteoblastic differentiation.     

Semiclassical dynamics and coherent soliton condensates in self-focusing nonlinear media with periodic initial conditions

The semiclassical (small dispersion) limit of the focusing nonlinear Schrödinger equation with periodic initial conditions (ICs) is studied analytically and numerically. First, through a comprehensive set of numerical simulations, it is demonstrated that solutions arising from a certain class of ICs, referred to as “periodic single-lobe” potentials, share the same qualitative features, which also coincide with those of solutions arising from localized ICs. The spectrum of the associated scattering problem in each of these cases is then numerically computed, and it is shown that such spectrum is confined to the real and imaginary axes of the spectral variable in the semiclassical limit. This implies that all nonlinear excitations emerging from the input have zero velocity, and form a coherent nonlinear condensate. Finally, by employing a formal Wentzel-Kramers-Brillouin expansion for the scattering eigenfunctions, asymptotic expressions for the number and location of the bands and gaps in the spectrum are obtained, as well as corresponding expressions for the relative band widths and the number of “effective solitons.” These results are shown to be in excellent agreement with those from direct numerical computation of the eigenfunctions. In particular, a scaling law is obtained showing that the number of effective solitons is inversely proportional to the small dispersion parameter.     

A nonlinear partial least squares algorithm using quadratic fuzzy inference system

We introduce a new nonlinear partial least squares algorithm ‘Quadratic Fuzzy PLS (QFPLS)’ that combines the outer linear Partial Least Squares (PLS) framework and the Takagi–Sugeno–Kang (TSK) fuzzy inference system. The inner relation between the input and the output PLS score vectors is modeled by a quadratic TSK fuzzy inference system. The performance of the proposed QFPLS method is tested and compared against four other well‐known partial least squares methods (Linear PLS (LPLS), Quadratic PLS (QPLS), Linear Fuzzy PLS (LFPLS), and Neural Network PLS (NNPLS)) on various different types of randomly generated test data. QFPLS outperformed competitors based on two comparison measures: the output variables cumulative per cent variance captured by the PLS latent variables and the root mean‐square error of prediction (RMSEP). Copyright © 2009 John Wiley & Sons, Ltd.     

Linearizable boundary value problems for the nonlinear Schrödinger equation in laboratory coordinates

Boundary value problems for the nonlinear Schrödinger equation on the half line in laboratory coordinates are considered. A class of boundary conditions that lead to linearizable problems is identified by introducing appropriate extensions to initial-value problems on the infinite line, either explicitly or by constructing a suitable Bäcklund transformation. Various soliton solutions are explicitly constructed and studied.     

Activation and Deactivation of Benzylic C−H Bonds Guided by Stereoelectronic Effects in Hydrogen Atom Transfer from Amides and Amines to Alkoxyl Radicals

Kinetic and product studies on the reactions of tert-alkoxyl radicals with secondary and tertiary alkanamides bearing benzylic α-C−H bonds, isoindoline, tetrahydroisoquinoline and the corresponding N-acetyl derivatives were carried out. Product studies on the reactions with the tert-butoxyl radical (tBuO⋅) point toward exclusive HAT from the benzylic α-C−H bonds. Comparison of the k_H values measured for reaction with the cumyloxyl radical (CumO⋅) with those obtained previously for the corresponding reactions of N-alkyl- and N,N-dialkylalkanamides, are indicative of a lack of benzylic activation and the operation of steric and stereoelectronic effects. Compared to N-methyl and N-ethyl groups, the presence of N-benzyl groups increases the barrier required to reach the optimal conformation for HAT, where the α-C−H bond to be cleaved is perpendicular to the plane of the amide, precluding concurrent overlap with the phenyl π-system. When the benzylic α-C−H bonds are in a conformation that allows for optimal overlap with both the phenyl π-system and the amide π-system or amine nitrogen lone pair, as in the isoindoline and tetrahydroisoquinoline derivatives, increases in k_H that exceed 2-orders of magnitude were observed, highlighting the strong contribution provided by stereoelectronic activation to these HAT processes.