An NMR study of the interaction between Melanin Free Acid and Mn ions as a model to mimic the enhanced proton relaxation rates in melanotic melanoma

The interaction of a soluble Melanin Free Acid (MFA) from Sepia melanin with Mn²⁺ ions is investigated by measuring the proton water relaxation rates. The similarity between MFA and the parent melanin is assessed by means of their high resolution ¹³C cross polarization magic angle spinning NMR spectra. The observed marked increase in longitudinal proton relaxation rates and the characteristic 1/T₁ NMRD profile are associated to the formation of a macromolecular metal complex. The presence of similar paramagnetic species is expected to cause the high contrast shown by melanotic tissues in MRI.     

Conformational energy contribution to the heat of solution in polymer–solvent systems. Part I. Theory

The conformational energy contribution (ΔU_conf) to the heat of solution in polymer-solvent systems is presented and discussed in connection with chain conformational properties. In particular, ΔU_conf has been discussed in terms of various possible mechanisms of coil deformation.     

Non-cylindrical symmetry of the ordering matrix of some spectroscopic probes in a lyotropic mesophase studied by 2H N.M.R. spectroscopy

Deuterium N.M.R. spectroscopy has been used to investigate the orientational ordering of perdeuteriated naphthalene and two perdeuteriated fluorescent probes (pyrene and perylene) dissolved in a discotic nematic micellar phase of potassium laurate/potassium chloride/decanol/water. The results show that the ordering tensors of these probes are not cylindrically symmetric.     

Crystal structure of a seven-coordinate cobalt(II) complex with a new polyfunctional hydrazonic ligand, [Co(H4dapis)(OH2)2]Cl2·9/2H2O

A seven-coordinate cobalt(II) complex has been synthesized with a new hydrazonic ligand, H₄dapis, and its crystal structure determined by X-ray diffraction methods and refined toR 0.0564 for 2763 independent reflections. The structure consists of [Co(H₄dapis)(OH₂)2] cations, Cl anions, and lattice H₂O molecules interlinked by hydrogen bonds. The cobalt atom has a distorted pentagonal bipyramidal environment with two axial H₂O molecules and the H₄dapis ligand forming the basal plane.     

A supramolecular copper(II) compound with double bridging water ligands: synthesis, crystal structure, spectroscopy, thermal analysis, and magnetism

A complex of composition {[{Cu(NDC)(OH₂)(tn)(μ-OH₂)}₂]·2H₂O}_∞ (1) and a mononuclear complex salt [Cu(OH₂)₂(tn)₂](NDC)·3H₂O (2), where NDC = 2,6-naphthalenedicarboxylate dianion and tn = 1,3-diaminopropane, were simultaneously crystallized from an aqueous solution of the copper(II) naphthalenedicarboxylate—1,3-diaminopropane—methanol system. The crystal and molecular structures of both complexes were determined by single-crystal X-ray diffraction. Compound (1) consists of a supramolecular coordination complex in which the monomeric unit is assembled from a homodinuclear Cu(II) bridged by two water ligands. The Cu(II) centers exhibit distorted octahedral coordination; the equatorial plane is provided by one chelating tn ligand, one NDC^2? ligand, one μ-H₂O while the axial positions are occupied by H₂O and μ-H₂O. Strong intra- and/or intermolecular hydrogen bonds, also involving the crystallization water molecules, together with π–π stacking interactions, are involved in building up the supramolecule. The solid structure of compound (2) includes three water molecules of crystallization, the counter ion NDC^2?, and a Cu(II) cationic complex in which the metal is six-coordinated in an axially elongated octahedron defined by two chelating tn ligands in the equatorial plane and two water ligands in the axial positions. Thermal analyses of (1) show two significant weight losses corresponding to water molecules (lattice and coordinated), followed by the decomposition of the network.     

Glow wire ignition temperature (GWIT) and comparative tracking index (CTI) of glass fibre filled engineering polymers, blends and flame retarded formulations

Engineering thermoplastic polymers such as polyamides, polycarbonates, semi-crystalline aromatic polyesters and their blends are widely used as insulating materials in electrical and electronic appliances. Flame retardants are often employed in the formulation of these materials, since good performance in terms of ignition and tracking resistance, evaluated by Glow Wire Tests (GWIT) and Comparative Tracking Index (CTI) are required in these applications. In this paper, a comparative evaluation of GWIT and CTI performances has been simultaneously performed for a wide set of glass fibre filled materials chosen among engineering thermoplastics and their blends. Some flame retarded formulations have been also tested, in order to screen the effects of various additives. Useful indications have been obtained on the effect of each polymer and additives on GWIT and CTI properties. In addition, interesting synergies have been observed, especially by blending polyesters and polyamides. Thermogravimetric measurements of char yields have been successfully related with CTI behaviour. The presence of additives changes the structure of the carbonaceous residue, hence the conductivity of the tracks. Neat polycarbonate passed the GWIT test but not CTI, while poly(butylene terephthalate) showed the best balance of GWIT and CTI performance among the pure resins tested. Blending polycarbonate with polyester did not improve significantly GWIT performance, but had a negative effect on tracking resistance. Polyesters/polyamide blends were dominated by polyester in GWIT, but they showed synergistic effects in CTI.     

Synthesis and application of ortho-palladated complex of (4-phenylbenzoylmethylene)triphenylphosphorane as a highly active catalyst in the Suzuki cross-coupling reaction

The ortho-metallated complex [Pd(μ-Cl){κ₂(C,C)-[C₆H₄(PPh₂CHC(O)C₆H₄-Ph-4)}]₂ (2a) was prepared by refluxing of Pd(OAc)₂ and {(Ph)₃PCHCOC₆H₄-Ph-4} (PhBPPY) of in CH₂Cl₂ followed by addition of an excess of KCl in MeOH Complex (2a) reacts with triphenylphosphine to give the mononuclear derivative [Pd(Cl)(PhC₆H₄COCHPPh₂C₆H₄)(PPh₃)] (3a) whose crystal structure has been determined by single crystal X-ray diffraction. The Suzuki reactions of aryl bromides and chlorides of varying electron density using complex (3a) as an efficient catalyst were performed, giving the cross-coupling products in good to excellent yields.     

Characterization of primary amine capped CdSe, ZnSe, and ZnS quantum dots by FT-IR: determination of surface bonding interaction and identification of selective desorption

Surface ligands of semiconductor quantum dots (QDs) critically influence their properties and functionalities. It is of strong interest to understand the structural characteristics of surface ligands and how they interact with the QDs. Three quantum dot (QD) systems (CdSe, ZnSe, and ZnS) with primary aliphatic amine capping ligands were characterized primarily by FT-IR spectroscopy as well as NMR, UV-vis, and fluorescence spectroscopy, and by transmission electron microscopy (TEM). Representative primary amines ranging from 8 to 16 carbons were examined in the vapor phase, KBr pellet, and neat and were compared to the QD samples. The strongest hydrogen-bonding effects of the adsorbed ligands were observed in CdSe QDs with the weakest observed in ZnS QDs. There was an observed splitting of the N-H scissoring mode from 1610 cm(-1) in the neat sample to 1544 and 1635 cm(-1) when bound to CdSe QDs, which had the largest splitting of this type. The splitting is attributed to amine ligands bound to either Cd or Se surface sites, respectively. The effect of exposure of the QDs dispersed in nonpolar medium to methanol as a crashing agent was also examined. In the CdSe system, the Cd-bound scissoring mode disappeared, possibly due to methanol replacing surface cadmium sites. The opposite was observed for ZnSe QDs, in which the Se-bound scissoring mode disappeared. It was concluded that surface coverage and ligand bonding partners could be characterized by FT-IR and that selective removal of surface ligands could be achieved through introduction of competitive binding interactions at the surface.