Functionalised β-diketonate polynuclear lanthanoid hydroxo clusters: Synthesis,characterisation, and magnetic properties

The controlled hydrolysis of lanthanoid trichloride hexahydrate (Ln = Nd, Eu, Ho) in methanol with the β-diketone ligands dibenzoylmethane and 1,3-bis(4-ethoxyphenyl)propane-1,3-dione yielded tetranuclear and pentanuclear hydroxo clusters for Eu and Ho. In contrast, performing the reaction in the presence of 1,3-bis(4-methoxyphenyl)propane-1,3-dione yielded a mononuclear complex for Nd. The compounds were structurally characterised by means of single crystal X-ray diffraction, showing that the increased bulkiness of the ligand due to the ethoxy functionalities does not affect the capability of the diketonate to stabilize the cluster core. Variable temperature dc susceptibility magnetic measurements were made on the clusters and were indicative of very weak to zero antiferromagnetic, intra-cluster coupling. Variable frequency ac data recorded at low temperatures did not show any evidence for single molecule magnet (SMM) behaviour, unlike the recent reported case of the analogue [Dy₅(OH)₅(Ph₂acac)₁₀], where Ph₂acac⁻ is the dibenzoylmethanide ligand.     

All‐Optical Integrated Logic Operations Based on Chemical Communication between Molecular Switches

Molecular logic gates process physical or chemical “inputs” to generate “outputs” based on a set of logical operators. We report the design and operation of a chemical ensemble in solution that behaves as integrated AND, OR, and XNOR gates with optical input and output signals. The ensemble is composed of a reversible merocyanine‐type photoacid and a ruthenium polypyridine complex that functions as a pH‐controlled three‐state luminescent switch. The light‐triggered release of protons from the photoacid is used to control the state of the transition‐metal complex. Therefore, the two molecular switching devices communicate with one another through the exchange of ionic signals. By means of such a double (optical–chemical–optical) signal‐transduction mechanism, inputs of violet light modulate a luminescence output in the red/far‐red region of the visible spectrum. Nondestructive reading is guaranteed because the green light used for excitation in the photoluminescence experiments does not affect the state of the gate. The reset is thermally driven and, thus, does not involve the addition of chemicals and accumulation of byproducts. Owing to its reversibility and stability, this molecular device can afford many cycles of digital operation.     

Use of near infrared emission spectroscopy in the study of supporting materials and stationary phases for liquid chromatography

Near infrared emission spectroscopy (NIRES) has been investigated in the study of different materials employed in liquid chromatography. The samples were heated in a nitrogen atmosphere and the emission spectra were obtained using a lab-made NIRES instrument. Through principal component analysis (PCA) using the raw emission spectra, it was possible to distinguish different materials according to their physical and/or chemical characteristics. Linear relationships between emissivity spectra and the contents of the coating material or the specific surface areas was observed for stationary phases or bare silicas, respectively. Furthermore, the thermal stability of stationary phases could be followed in real time.     

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.     

The pretzelosity TMD and quark orbital angular momentum

We study the connection between the quark orbital angular momentum and the pretzelosity transverse-momentum dependent parton distribution function. We discuss the origin of this relation in quark models, identifying as key ingredient for its validity the assumption of spherical symmetry for the nucleon in its rest frame. Finally we show that the individual quark contributions to the orbital angular momentum obtained from this relation cannot be interpreted as the intrinsic contributions, but include the contribution from the transverse centre of momentum which cancels out only in the total orbital angular momentum.     

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.