25 research outputs found

    Development of lanthanide probes for cellular imaging

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    Luminescent complexes of europium and terbium, incorporating new sensitizing chromophore moieties containing carboxylic acid functional groups, have been synthesised. It has been shown that the new tetraazatriphenylene chromophore leads to highly emissive complexes. A thiaxanthone chromophore, despite sensitizing lanthanide emission, results in complexes with lower quantum yields and is only practically useful for europium. Modification of the azaxanthone chromophore by formation of its N-oxide was investigated as a possibility of extending its longest wavelength absorption maximum beyond 340 nm. Phosphinate pendant arms were introduced into complexes containing the azaxanthone chromophore and resulted in highly emissive complexes Complexes of the new chromophores were investigated, together with numerous further examples, in terms of their susceptibility to quenching by electron rich species (iodide, ascorbate, urate). These experiments enhanced the mechanistic understanding of this process. Complexes using an azaxanthone chromophore with a carboxylic function and phenyl amide arms were used in coupling reactions. The coupling reactions involved isolation of the NHS ester of the complex. Cellular uptake and cytotoxicity experiments were carried out with several of these conjugate complexes. The possibility to observe these complexes using two photon excitation fluorescence microscopy was demonstrated

    Effect of the composition of hybrid sands on the change in thermal expansion

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    In the foundry industry, silica sands are the most commonly used type of sands for the production of sand foundry moulds using various types of binders. Their greatest disadvantage is their significant volume changes at elevated temperatures, which are associated with the formation of many foundry defects from stress, such as veining, and thus have a direct influence on the final quality of the casting. In the case of non-silica sands and synthetic sands, the volume stability is more pronounced, but this is accompanied by a higher purchase price. Therefore, a combination of silica sand and synthetic sand CERABEADS is considered in order to influence and reduce the thermal expansion. The hybrid mixtures of sands, and their most suitable ratios, were evaluated in detail using sieve analysis, log W and cumulative curve of granularity. It was found that the addition of 50% CERABEADS achieves a 32.2% reduction in dilatation but may increase the risk of higher stresses. The measurements showed a significant effect of the granulometric composition of the sand on the resulting thermal expansion, where the choice of grain size and sorting can achieve a significant reduction in dilatation with a small addition of CERABEADS.Web of Science1517art. no. 618

    Crystal structure of trans-bis{4-bromo-N-[(pyridin-2-yl)methylidene]aniline-κ2N,N′}dichloridoruthenium(II)

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    In the title complex, [RuCl2(C12H9BrN2)2] or [RuCl2(PM-BrA)2] (PM-BrA = 4-bromo-N-(2′-pyridylmethylene)aniline), the RuII cation is located on a centre of inversion and is surrounded by four N atoms of two PM-BrA ligands in the equatorial plane and by two Cl atoms in a trans axial arrangement, displaying a distorted octahedral coordination environment. Two C atoms in the benzene ring of the PM-BrA ligand are equally disordered over two sets of sites. The benzene and pyridine rings of the PM-BrA ligand are oriented at dihedral angles of 62.1 (10) and 73.7 (11)° under consideration of the two orientations of the disordered benzene ring. In the crystal, the complex molecules are connected via C—H...Cl hydrogen-bonding interactions into a layered arrangement parallel (100). C—H...Br hydrogen bonding and weak aromatic π–π stacking interactions complete a three-dimensional supramolecular network

    Crystal structure of diaquatris(benzohydrazide-κ2N,O)(isophthalato-κO)samarium(III) nitrate

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    The first benzohydrazide complex of a lanthanide is reported. In the title compound, [Sm(C8H4O4)(C7H8N2O)3(H2O)2]NO3, systematic name diaquatris(benzohydrazide-κ2N,O)(isophthalato-κO)samarium(III) nitrate, the SmIII ion is nine-coordinated in a distorted tricapped trigonal–prismatic geometry by three oxygen atoms and three nitrogen atoms from three benzhydrazide (bzz) ligands, one oxygen atom from the isophthalate (itp2−) ligand, and two oxygen atoms from coordinated water molecules. The nitrate group is disordered over two sets of sites with occupancy factors of 0.310 (17) and 0.690 (17). In the crystal, adjacent molecules are linked into chains via pairs of O—H...O and N—H...O hydrogen bonds between the carboxylate acceptor and the coordinated water and amine NH2 donors. Molecules are further stacked by π–π interactions involving the benzene ring of the itp2− ligands, forming double chains that extend in the b-axis direction. These double chains are further linked into a three-dimensional supramolecular network via hydrogen bonds (O—H...O, N—H...O and C—H...O) between the complex molecule and the nitrate groups along with C—H...π and π–π interactions involving the benzene rings of the bzz and itp2− ligands

    Crystal structure of a mixed-ligand terbium(III) coordination polymer containing oxalate and formate ligands, having a three-dimensional fcu topology

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    The title compound, poly[(μ3-formato)(μ4-oxalato)terbium(III)], [Tb(CHO2)(C2O4)]n, is a three-dimensional coordination polymer, and is isotypic with the LaIII, CeIII and SmIII analogues. The asymmetric unit contains one TbIII ion, one formate anion (CHO2−) and half of an oxalate anion (C2O42−), the latter being completed by application of inversion symmetry. The TbIII ion is nine-coordinated in a distorted tricapped trigonal–prismatic manner by two chelating carboxylate groups from two C2O42− ligands, two carboxylate oxygen atoms from another two C2O42− ligands and three oxygen atoms from three CHO2− ligands, with the Tb—O bond lengths and the O—Tb—O bond angles ranging from 2.4165 (19) to 2.478 (3) Å and 64.53 (6) to 144.49 (4)°, respectively. The CHO2− and C2O42− anions adopt μ3-bridging and μ4-chelating-bridging coordination modes, respectively, linking adjacent TbIII ions into a three-dimensional 12-connected fcu topology with point symbol (324.436.56). The title compound exhibits thermal stability up to 623 K, and also displays strong green photoluminescence in the solid state at room temperature

    Synthesis and investigation of a tris-cyclometalated iridium complex bearing a single quarternary ammonium group

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    A novel tris-cyclometalated iridium complex (1) containing a single quarternary ammonium moiety has been synthesized, characterized, and investigated as a potential cellular imaging probe. The complex is the next generation of the aminoalkyl iridium complexes recently published by our group. The complex possesses outstanding photophysical properties. The complex is stable in solution in dark but exhibits rapid photocatalyzed transformations. Investigations of this behavior have shown that these transformations involve the formation of an electrophilic species, which can be captured by a suitable nucleophile, leading to the formation of new product. The complex has also been investigated as a potential cellular stain. It is less cytotoxic than its aminoalkyl predecessor and shows lysosomal localization as its precursor

    Crystal structure of fac-{5-[(hexylazaniumyl)methyl]-2-(pyridin-2-yl)phenyl-κ2N,C1}bis[2-(pyridin-2-yl)phenyl-κ2N,C1]iridium(III) chloride

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    The asymmetric unit of the title compound, fac-[Ir(C11H8N)2(C18H24N2)]Cl or fac-[Ir(ppy)2(Hppy-NC6)]Cl, contains two [Ir(ppy)2(ppy-NC6)](H+) cations, two Cl− anions and disordered solvent. In each complex molecule, the IrIII ion is coordinated by two C,N-bidentate 2-(pyridin-2-yl)phenyl ligands and one C,N-bidentate N-[4-(pyridin-2-yl)benzyl]hexan-1-aminium ligand, leading to a distorted fac-octahedral coordination environment. In the crystal, the molecules are linked by N—H...Cl, C—H...π and π–π interactions, forming a three-dimensional supramolecular structure. The hexyl group of one molecule is disordered over two orientations with a refined occupancy ratio of 0.412 (13):0.588 (13). The acetone and hexane solvent molecules were found to be highly disordered and their contribution to the scattering was masked using the solvent-masking routine smtbx.mask in OLEX2 [Rees et al. (2005). Acta Cryst. D61, 1299–1301]. These solvent molecules are not considered in the given chemical formula and other crystal data
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