Synthesis, multiphase characterization, and helicity control in chiral DACH-linked oligothiophenes

A new class of chiral oligothiophenes is described. Mono-, bi-, ter-, and quarterthiophenes have been linked to enantiopure trans-1,2-cyclohexanediamine (DACH) via diamino or diimino moieties. The stereochemistry of DACH, the type of linker, and oligothiophene size determine the conformational flexibility of these molecules and consequently their molecular and supramolecular helicity in solution and in the solid state. The case of diaminobis(bithiophene), which inverts helicity and shows chiral amplification in the transition from solution to film, is described in detail. Based on the combined use of circular dichroism in solution and in the solid state, single-crystal/thin-film X-ray diffraction, and polarized optical microscopy, a working mechanism has been proposed to explain this unexpected behavior.     

Layered Na(0.71)CoO(2): a powerful candidate for viable and high performance Na-batteries

The present study reports on the synthesis and the electrochemical behavior of Na(0.71)CoO(2), a promising candidate as cathode for Na-based batteries. The material was obtained in two different morphologies by a double-step route, which is cheap and easy to scale up: the hydrothermal synthesis to produce Co(3)O(4) with tailored and nanometric morphology, followed by the solid-state reaction with NaOH, or alternatively with Na(2)CO(3), to promote Na intercalation. Both products are highly crystalline and have the P2-Na(0.71)CoO(2) crystal phase, but differ in the respective morphologies. The material obtained from Na(2)CO(3) have a narrow particle length (edge to edge) distribution and 2D platelet morphology, while those from NaOH exhibit large microcrystals, irregular in shape, with broad particle length distribution and undefined exposed surfaces. Electrochemical analysis shows the good performances of these materials as a positive electrode for Na-ion half cells. In particular, Na(0.71)CoO(2) thin microplatelets exhibit the best behavior with stable discharge specific capacities of 120 and 80 mAh g(-1) at 5 and 40 mA g(-1), respectively, in the range 2.0-3.9 V vs. Na(+)/Na. These outstanding properties make this material a promising candidate to construct viable and high-performance Na-based batteries.     

Status and perspectives in thin films and patterning of spin crossover compounds

Spin crossover compounds are a class of functional materials able to switch their spin state upon external stimuli. They were proposed as potential candidates for several technological applications that require highly controlled thin films and patterns. Here we present a critical overview of the most important approaches for thin film growth and patterning of spin-crossover compounds, giving special attention to Fe(ii) based molecules, which are the most studied materials. We present both conventional approaches to thin film growth (Langmuir-Blodgett, constructive chemical approach, spin coating, drop casting and vacuum sublimation) and patterning (combined top-down/bottom-up method, soft and unconventional lithography). We critically discuss the application of thin film growth and fabrication techniques highlighting the most critical aspects and the perspectives opened by the recent progress.     

Mn(II) and Zn(II) interactions with peptide fragments from Parkinson's disease genes

Two peptide sequences from PARK9 Parkinson's disease gene, ProAspGluLysHisGluLeu, (P(1)D(2)E(3)K(4)H(5)E(6)L(7)) (1) and PheCysGlyAspGlyAlaAsnAspCysGly (F(1)C(2)G(3)D(4)G(5)A(6)N(7)D(8)C(9)G(10)) (2) were tested for Mn(II), Zn(II) and Ca(II) binding. The fragments are located from residues 1165 to 1171 and 1184 to 1193 in the PARK9 encoded protein. This protein can protect cells from poisoning of manganese, which is an environmental risk factor for a Parkinson's disease-like syndrome. Mono- and bi-dimensional NMR spectroscopy has been used to understand the details of metal binding sites at different pH values and at different ligand to metal molar ratios. Mn(II) and Zn(II) coordination with peptide (1) involves imidazole N(ε) or N(δ) of His(5) and carboxyl γ-O of Asp(2), Glu(3) and Glu(6) residues. Six donor atoms participate in Mn(II) binding resulting in a distorted octahedral geometry, possibly involving bidentate interaction of carboxyl groups; four donor atoms participate in Zn(II) binding resulting in a tetracoordinate geometry. Mn(II) and Zn(II) coordination involves the two cysteine residues with peptide (2); Mn(II) accepts additional ligand bonds from the carboxyl γ-O of Asp(4) and Asp(8) to complete the coordination sphere; the unoccupied sites may contain solvent molecules. The failure of Ca(II) ions to bind to either peptide (1) or (2) appears to result, under our conditions, from the absence of chelating properties in the chosen fragments.     

Does adsorption at hydroxyapatite surfaces induce peptide folding? Insights from large-scale B3LYP calculations

Large-scale periodic quantum mechanical calculations (509 atoms, 7852 atomic orbitals) based on the hybrid B3LYP functional focused on the peptide folding induced by the adsorption on the (001) and (010) hydroxyapatite (HA) surfaces give interesting insights on the role of specific interactions between surface sites and the peptide, which stabilize the helix conformation over the "native" random coil ones for in silico designed model peptides. The two peptides were derived from the 12-Gly oligomer, with one (P1, C-tGGKGGGGGGEGGN-t) and two (P2, C-tGGKGGKEGGEGGN-t) glutamic acid (E) and lysine (K) residue mutations. The most stable gas-phase "native" conformation for both peptides resulted in a random coil (RC) structure, with the helix (H) conformation being ≈100 kJ mol(-1) higher in free energy. The two peptide conformations interact with the HA (001) and (010) surfaces by C═O groups via Ca(2+) ions, by hydrogen bond between NH(2) groups and the basic PO(4)(3-) groups and by a relevant fraction due to dispersion forces. Peptide adsorption was studied on the dry (001) surface, the wet one envisaging 2 H(2)O per surface Ca(2+) and, on the latter, also considering the adsorption of microsolvated peptides with 4 H(2)O molecules located at sites responsible of the interaction with the surface. The P1 mutant does prefer to be adsorbed as a random coil by ≈160 kJ/mol, whereas the reverse is computed for P2, preferring the helix conformation by ≈50 kJ/mol. Adsorption as helix of both P1 and P2 mutants brings about proton transfer toward the HA surfaces with a large charge transfer component to the interaction energy.     

Gravitational instability of the primordial plasma: Anisotropic evolution of structure seeds

We study how the presence of a background magnetic field, of intensity compatible with current observation constraints, affects the linear evolution of cosmological density perturbations at scales below the Hubble radius. The magnetic field provides an additional pressure that can prevent the growth of a given perturbation; however, the magnetic pressure is confined only to the plane orthogonal the field. As a result, the “Jeans length” of the system not only depends on the wavelength of the fluctuation but also on its direction, and the perturbative evolution is anisotropic. We derive this result analytically and back it up with direct numerical integration of the relevant ideal magnetohydrodynamics equations during the matter-dominated era. Before recombination, the kinetic pressure dominates and the perturbations evolve in the standard way, whereas after that time magnetic pressure dominates and we observe the anisotropic evolution. We quantify this effect by estimating the eccentricity ?   of a Gaussian perturbation in the coordinate space that was spherically symmetric at recombination. For a perturbations at the sub-galactic scale, we find that ?=0.7$?=0.7$ at z=10$z=10$ taking the background magnetic field of order 10⁻⁹${10}^{-9}$ gauss.     

Managing longevity and disability risks in life annuities with long term care

The aim of the paper is twofold. Firstly, it develops a model for risk assessment in a portfolio of life annuities with long term care benefits. These products are usually represented by a Markovian Multi-State model and are affected by both longevity and disability risks. Here, a stochastic projection model is proposed in order to represent the future evolution of mortality and disability transition intensities. Data from the Italian National Institute of Social Security (INPS) and from Human Mortality Database (HMD) are used to estimate the model parameters. Secondly, it investigates the solvency in a portfolio of enhanced pensions. To this aim a risk model based on the portfolio risk reserve is proposed and different rules to calculate solvency capital requirements for life underwriting risk are examined. Such rules are then compared with the standard formula proposed by the Solvency II project.     

Cyclochiral resorcin[4]arenes as effective enantioselectors in the gas phase

The effect of cyclochirality of rccc‐2,8,14,20‐tetra‐n‐decyl‐4,10,16,22‐tetra‐O‐methylresorcin[4]arene (C) on the enantiodiscrimination of a number of chiral bidentate and tridentate aromatic and aliphatic biomolecules (G) has been investigated by nano‐electrospray ionization (nano‐ESI)‐Fourier transform ion cyclotron resonance mass spectrometry. The experimental approach is based on the formation of diastereomeric proton‐bound [C·H·G]⁺ complexes by nano‐ESI of solutions containing an equimolar amount of quasi‐enantiomers (C) together with the chiral guest (G) and the subsequent measurement of the rate of the G substitution by the attack of several achiral and chiral amines. In general, the heterochiral complexes react faster than the homochiral ones, except when G is an aminoalcoholic neurotransmitter whose complexes, beyond that, exhibit the highest enantioselectivity. The kinetic results were further supported by both collision‐induced dissociation experiments on some of the relevant [C₂·H·G]⁺ three‐body species and Density functional theory (DFT) calculations performed on the most selective systems. Copyright © 2012 John Wiley & Sons, Ltd.     

Sobolev Periodic Solutions of Nonlinear Wave Equations in Higher Spatial Dimensions

We prove the existence of Cantor families of periodic solutions for nonlinear wave equations in higher spatial dimensions with periodic boundary conditions. We study both forced and autonomous PDEs. In the latter case our theorems generalize previous results of Bourgain to more general nonlinearities of class C ^k and assuming weaker non-resonance conditions. Our solutions have Sobolev regularity both in time and space. The proofs are based on a differentiable Nash–Moser iteration scheme, where it is sufficient to get estimates of interpolation-type for the inverse linearized operators. Our approach works also in presence of very large “clusters of small divisors”.     

A closure approximation for nematic liquid crystals based on the canonical distribution subspace theory

 A closure approximation for nematic polymers is presented. It approximates the fourth rank order tensor in terms of lower rank tensors, and is derived in the framework of the canonical distribution subspace theory. This approach requires a choice of the class of distributions: Here the set of Bingham distributions is chosen, as already introduced by Chaubal and Leal (1998). The closure is written in a generic frame of reference, and in an explicit form, so that it can be easily implemented. Such formulation also permits studying the closure approximation with continuation tools, which rather completely describe the system dynamics. The predictions can then be compared with those obtained with the exact model. The shear flow is considered as a test, since this flow condition appears to be the most demanding for closure approximations for nematic polymers. Received: 30 November 1999/Accepted: 30 November 1999