Excellent correlation between cathepsin B inhibition and cytotoxicity for a series of palladacycles

The reaction of the five- or six-membered C,N or C,S-palladacycles [(L)PdCl](2) with PTA (1,3,5-triaza-7-phosphaadamantane) led to the monomeric complexes [(L)Pd(PTA)Cl] 6a, 6b and 7 where LH= N,N-dimethyl-1-phenylmethanamine, benzyl(methyl)sulfane or 1-methyl-5-phenyl-1H-benzo[e][1,4]diazepin-2(3H)-one respectively. Dimeric complexes have also been synthesised: [Pd(2)L(2)(mu-dppe)Cl(2)], where LH = 1-methyl-5-phenyl-1H-benzo[e][1,4]diazepin-2(3H)-one (1a), (R)- or (S)-3-isopropyl-1-methyl-5-phenyl-1H-benzo[e][1,4]diazepin-2(3H)-one (1b, 1c), [Pd(2)L(2)(mu-dppf)Cl(2)], where L= 1-methyl-5-phenyl-1H-benzo[e][1,4]diazepin-2(3H)-one (4a) or (R)-3-isopropyl-1-methyl-5-phenyl-1H-benzo[e][1,4]diazepin-2(3H)-one (4b), respectively, and dppe = 1,2-bis(diphenylphosphino)ethane, dppf = 1,1'-bis(diphenylphosphino)ferrocene. The complexes were characterised in solution, by (1)H and (31)P NMR spectroscopy, and single crystals of complexes 6b and 7 were studied in the solid state by X-ray crystallography. The palladacycles were evaluated for in vitro activity as cytotoxic agents on A2780/S cells and also as cathepsin B inhibitors, an enzyme implicated in a number of cancer related events.

Thickness independence of true phase transition temperatures in barium strontium titanate films

The functional properties of two types of barium strontium titanate (BST) thin film capacitor structures were studied: one set of structures was made using pulsed-laser deposition (PLD) and the other using chemical solution deposition. While initial observations on PLD films looking at the behavior of T-m (the temperature at which the maximum dielectric constant was observed) and T-c(*) (from Curie-Weiss analysis) suggested that the paraelectric-ferroelectric phase transition was progressively depressed in temperature as BST film thickness was reduced, further work suggested that this was not the case. Rather, it appears that the temperatures at which phase transitions occur in the thin films are independent of film thickness. Further, the fact that in many cases three transitions are observable, suggests that the sequence of symmetry transitions that occur in the thin films are the same as in bulk single crystals. This new observation could have implications for the validity of the theoretically produced thin film phase diagrams derived by Pertsev [Phys. Rev. Lett. 80, 1988 (1998)] and extended by Ban and Alpay [J. Appl. Phys. 91, 9288 (2002)]. In addition, the fact that T-m measured for virgin films does not correlate well with the inherent phase transition behavior, suggests that the use of T-m alone to infer information about the thermodynamics of thin film capacitor behavior, may not be sufficient. (C) 2004 American Institute of Physics.

Intrinsic dielectric response in ferroelectric nano-capacitors

Measurements on 'free-standing' single-crystal barium titanate capacitors with thickness down to 75 nm show a dielectric response typical of large single crystals, rather than conventional thin films. There is a notable absence of any broadening or temperature shift of the dielectric peak or loss tangent. Peak dielectric constants of similar to25 000 are observed, and Curie-Weiss analysis demonstrates first order transformation behaviour. This is in dramatic contrast to results on conventionally deposited thin film capacitor heterostructures, which show large dielectric peak broadening and temperature shifts (e.g. Parker et al 2002 Appl. Phys. Lett. 81 340), as well as an apparent change in the nature-of the paraelectric-ferroelectric transition from first to second order. Our data are compatible with a recent model by Bratkovsky and Levanyuk (2004 Preprint cond-mat/0402100), which attributes dielectric peak broadening to gradient terms that will exist in any thin film capacitor heterostructure. The observed recovery of first order transformation behaviour is consistent with the absence of significant substrate clamping in our experiment, as modelled by Pertsev et al (1998,Phys. Rev. Lett. 80 1988), and illustrates that the second order behaviour seen in conventionally deposited thin films cannot be attributed to the effects of reduced dimensionality in the system, nor to the influence of an intrinsic universal interfacial capacitance associated with the electrode- ferroelectric interface.

YF[MoO4] and YCl[MoO4]: Two halide derivatives of yttrium ortho-oxomolybdate: Syntheses, structures, and luminescence properties

The halide derivatives of yttrium ortho-oxomolybdate YX[MoO4] (X = F, Cl) both crystallize in the monoclinic system with four formula units per unit cell. YF[MoO4] exhibits a primitive cell setting (space group P2(1)/c, a = 519.62(2) pm, b = 1225.14(7) pm, c = 663.30(3) pm, beta = 112.851(4)degrees), whereas the lattice of YCl[MoO4] shows face-centering (space group C2/m; a = 1019.02(5) pm, b = 720.67(4) pm, c = 681.50(3) pm, beta = 107.130(4)degrees). The two compounds each contain crystallographically unique Y3+ cations, which are found to have a coordination environment of six oxide and two halide anions. In the case of YF[MoO4], the coordination environment is seen as square antiprisms, and for YCl[MoO4], trigon-dodecahedra. are found. The discrete tetrahedral [MoO4](2-) units of the fluoride derivative are exclusively bound by six terminal Y3+ cations, while those of the chloride compound show a 5-fold coordination around the tetrahedra with one edge-bridging and four terminal Y3+ cations. The halide anions in each compound exhibit a coordination number of two, building up isolated planar rhombus-shaped units according to [Y2F2](4+) in YF[MoO4] and [Y2Cl2](4+) in YCl[MoO4], respectively. Both compounds were synthesized at high temperatures using Y2O3, MoO3, and the corresponding yttrium trihalide in a molar ratio of 1:3:1. Single crystals of both are insensitive to moist air and are found to be coarse shaped and colorless with optical band gaps situated in the near UV around 3.78 eV for the fluoride and 3.82 eV for the chloride derivative. Furthermore, YF[MoO4] seems to be a suitable material for doping to obtain luminescent materials because the Eu3+-doped compound shows an intense red luminescence, which has been spectroscopically investigated.

Mercuric bis(N-imino-methyl-formamidate), Hg(Imf)(2)

Single crystals of mercuric bis(N-imino-methyl-formamidate), Hg(Imf)(2), were obtained from aqueous solutions of 1,2,4-triazole and Hg(NO3)(2)center dot 2H(2)O. The crystal structure [monoclinic, P2(1)/c (no. 14), a = 499.6(2), b = 1051.2(4), c = 711.1(3) pm, beta = 117.55(1)degrees, Z = 2, R, for 890 reflections with I-0 > 2 sigma(I-0): 0.0369] contains linear centrosymmetric Hg(Imf)(2) molecules with Hg-N distances of only 203.5(7)pm. Two plus two intra- and intermolecular nitrogen atoms add to an effective coordination number of 6.

3,5-dimethyl-4-amino-1,2,4-triazole (Dat) as a tridentate ligand in the polymeric cations of [Ag-3(Dat)(2)](NO3)(3)

Colourless single crystals of [Ag-3(Dat)(2)](NO3)(3) were obtained from a reaction of silver(l) nitrate and 3,5-dimethyl-4-amino-1,2,4-triazole (Dat). In the crystal structure (orthorhombic, Fdd2, Z = 8, a = 1100.1(2), b = 3500.3(2), c = 1015.4(3) pm, R, = 0.0434) there are two crystallographically non-equivalent silver sites in a one (Ag1) to two ratio (Ag2). Both resemble linear N-Ag-N coordination although angles are 163 degrees and 144 degrees, respectively Each Dat ligand coordinates with the two ring nitrogen atoms at 216 to 219 pm and with one amino-nitrogen atom at 229 pro. According to the composition [Ag-3(Dat)(2)](3+) = [(Dat)Ag-3/2](3+), a polymeric structure is built with all Ag+ ions bridging.

The persistence of the HgCl2 molecule in five new compounds in the system (NH4)(w)HgxCly(H2O)(z) with w : x : y : z=1 : 5 : 11 : 0, 2 : 3 : 8 : 1, 4 : 3 : 10 : 2, 2 : 1 : 4 : 1, and 10 : 3 : 16 : 0

Five new compounds in the system (NH4)Cl/HgCl2/H2O have been obtained as colourless single crystals, (NH4)Hg5Cl11, (NH4)(2)Hg3Cl8(H2O), (NH4)(4)Hg3Cl10(H2O)(2), (NH4)(2)HgCl4(H2O), and (NH4)(10)Hg3Cl16. In all of these, as in HgCl2 itself, (almost) linear HgCl2 molecules persist with Hg-Cl distances varying from 229 to 236 pm. In (NH4)(10)Hg3Cl16 there are also tetrahedra [HgCl4] with d(Hg-Cl) = 247 pm present. If larger Hg-Cl distances (of up to 340 pm) are considered as belonging to the coordination sphere of Hg-II, the structures may be described as consisting of isolated octahedra and tetrahedra as in (NH4)(10)Hg3Cl16, edge-connected chains as in (NH4)(2)HgCl4(H2O), edge-connected chains and layers of octahedra as in (NH4)(4)Hg3Cl10(H2O)(2), corrugated layers of edge-connected octahedra as in (NH4)(2)Hg3Cl8(H2O), and, finally, a three-dimensional network of connected six- and seven-coordinate Hg-Cl polyhedra as in (NH4)Hg5Cl11. The water molecules are never attached to Hg-II. The (NH4)(+) cations, and sometimes Cl- anions, play a role for electroneutrality only.

Bis(trifluoromethyl)mercury(II) complexes with purine and 3,5-dimethyl-4 '-amino-triazole as ligands, [Hg(CF3)(2)(Pur)](4) and [Hg(CF3)(2)(Dat)](2)

Colourless single crystals of [Hg(CF3)(2)(Pur)](4) and [Hg(CF3)(2)(Dat)](2) were obtained from aqueous and etheric solutions of the respective components Purine, (imidazo[4,5-d]pyrimidine, Pur), 3,5-dimethyl-4 '-amino-triazole (Dat) and bis(trifluoromethyl)mercury(II), Hg(CF3)(2). [Hg(CF3)(2)(Pur)](4) crystallizes with the tetragonal system (P-4, Z = 8, a = 1486.8(2), c = 1026.2(l) pm, R-all = 0.0657) with tetrameric molecules consisting of four purine molecules bridged by slightly bent Hg(CF3)2 molecules forming a cage with the CF3 ligands surrounding this cage. The two modifications of [Hg(Dat)(CF3)2]2 (1: 170 K, triclinic, P-1, Z = 2, a 814.9(2), b = 845.4(2), c = 968.4(3) pm, alpha = 106.55(2)degrees, beta= 103.41(2)degrees, gamma = 110.79(2)degrees, R-all = 0.1189; II: monoclinic, P2(1)/c, Z = 8, a = 879.8(2), b = 1731.0(3), c = 1593.9(3) pm, beta = 106.89(2)degrees, R-all = 0.1199) both contain dimeric molecules that are stacked parallel to one crystal axis to strands which are arranged in a parallel fashion in I and rotated against each other in 11 by 110 degrees. In both, the tetrameric [Hg(CF3)(2)(Pur)](4) and the dimeric [Hg(CF3)(2)(Dat)](2) the Hg(CF3)(2) molecules are slightly bent (around 167 and 170 degrees) and rather weakly attached to the N-donor ligands Pur and Dat with Hg-N distances around 272 pm, although in both cases the Hg atoms bridge between two ligand molecules.

Pyrimidine and pyrazine as N-donor ligands in mercurous complexes: [Hg-2(Pym)]NO3)(2), [Hg-2(Pym)](ClO4)(2), and [Hg-2(Pyp)(2)](ClO4)(2)

Colourless single crystals of [Hg-2(Pym)](NO3)(2), [Hg-2(Pym)](ClO4)(2) and [Hg-2(Pyp)(2)](ClO4)(2) were obtained from aqueous solutions of the respective components Hg-2(NO3)(2).2H(2)O, Hg-2(ClO4)(2).6H(2)O, pyrimidine (Pym) and pyrazine (Pyp). The crystal structures were determined from single-crystal X-ray diffractometer data. [Hg-2(Pym)](NO3)(2): monoclinic, C2/c, Z = 8, a = 1607.4(2), b = 652.79(7), c = 2000.5(2) pm, beta = 103.42(2)degrees, R-all = 0.0530; [Hg-2(Pym)](ClO4)(2): orthorhombic, Pnma, Z = 4, a = 1182.7(2), b = 1662.5(2), c = 607.9(1) pm, R-all = 0.0438; [Hg-2(Pyp)(2)](ClO4)(2): orthorhombic, Aba2, Z = 4, a = 1529.39(9), b = 1047.10(14), c = 1133.49(15) pm, R-all = 0.0381. The crystal structures of [Hg-2(Pym)](NO3)(2) and [Hg-2(Pym)](ClO4)(2) contain polymeric cationic chains [Hg-2(Pym)](+) that are arranged to corrugated layers between which the anions are situated. [Hg-2(Pyp)(2)](ClO4)(2) consists of polymeric cationic layers that are built from (Hg-2)(2)(Hg-2)(2/2)(Pyp)(4) rings connected to each other; the perchlorate tetrahedra are located between these layers.

Formation of NH4[Hg-3(NH)(2)](NO3)(3) and transformation to [Hg2N](NO3)

NH4[Hg-3(NH)(2)](NO3)(3) (1) and [Hg2N](NO3) (2) are obtained from cone. aqueous ammonia solutions of Hg(NO3)(2) at ambient temperature and under hydrothermal conditions at 180 degreesC, respectively, as colourless and dark yellow to light brown single crystals. The crystal structures {NH4[Hg-3(NH)(2)](NO3)(3): cubic, P4(I)32, a = 1030.4(2) pm, Z = 4, R-all = 0.028; [Hg2N](NO3): tetragonal, P4(3)2(1)2, a = 1540.4(1), c = 909.8(1) pm, Z = 4, R-all = 0.054} have been determined from single crystal data. Both exhibit network type structures in which [HNHg3] and [NHg4] tetrahedra of the partial structures of 1 and 2 are connected via three and four vertices, respectively. 1 transforms at about 270 degreesC in a straightforward reaction to 2 whereby the decomposition products of NH4NO3 are set free. 2 decomposes at about 380 degreesC forming yellow HgO. Most certainly, I is identical with a mineral previously analyzed as

[Ag(NH3)(2)]ClO4: Crystal structures, phase transition, and vibrational spectra

[Ag(NH3)(2)](ClO4) is obtained from a solution of AgClO4 in cone. ammonia as colourless single crystals (orthorhombic, Pnmn, Z = 4, a = 795.2(1) pm, b 617.7(1) pm, c = 1298.2(2) pm, R-all = 0.0494). The structure consists of linearly coordinated cations, [Ag(NH3)(2)](+), stacked in a staggered conformation and of tetrahedral (ClO4)(-) anions. A first order phase transition was observed between 210 and 200 K and the crystal structure of the low-temperature modification (monoclinic. P2/m, Z = 4, a = 789.9(5) pm, b = 604.1(5) pm, c = 1290.4(5) pm, beta = 97.436(5)degrees, at 170 K, R-all = 0.0636) has also been solved. Spectroscopic investigations (IR/Raman) have been carried out and the assignment of the spectra is discussed.

Uranyl Complexes of Carboxyl-Functionalized Ionic Liquids

Uranium(VI) oxide has been dissolved in three different ionic liquids functionalized with a carboxyl group: betainium bis[trifluoromethyl)sulfonyl]imide, 1-(carboxymethyl)-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, and N-(carboxymethyl)-N-methylpyrrolidinium bis[(trifluoromethyl)sulfonyl]imide. The dissolution process results in the formation of uranyl complexes with zwitterionic carboxylate ligands and bis[trifluoromethyl)sulfonyl]imide (bistriflimide) counterions. An X-ray diffraction study on single crystals of the uranyl complexes revealed that the crystal structure strongly depends on the cationic core appended to the carboxylate groups. The betainium ionic liquid gives a dimeric uranyl complex, the imidazolium ionic liquid a monomeric complex, and the pyrrolidinium ionic liquid a one-dimensional polymeric uranyl complex, Extended X-ray absorption fine structure measurements have been performed on the betainium uranyl complex. The absorption and luminescence spectra of the uranyl betainium complex have been studied in the solid state and dissolved in water, in acetonitrile, and in the ionic liquid betainium bistriflimide. The carboxylate groups remain coordinated to uranyl in acetonitrile and in betainium bistriflimide but not in water.

Magnetisation of 2.6T in Gadolinium Thin Films

There is renewed interest in rare-earth elements and gadolinium in particular for a range of studies in coupling physics and applications. However, it is still apparent that synthesis impacts understanding of the intrinsic magnetic properties of thin gadolinium films, particularly for thicknesses of topicality. We report studies on 50nm thick nanogranular polycrystalline gadolinium thin films on SiO2 wafers that demonstrate single-crystal like behavior. The maximum in-plane saturation magnetization at 4K was found to be 4pMS4K = (2.61±0.26)T with a coercivity of HC4K = (160±5)Oe. A maximum Curie point of TC = (293±2)K was measured via zero-field-cooled - field-cooled magnetization measurements in close agreement with values reported in bulk single crystals. Our measurements revealed magnetic transitions at T1 = (12±2)K (as deposited samples) and T2 = (22±2)K (depositions on heated substrates) possibly arising from the interaction of paramagnetic fcc grains with their ferromagnetic hcp counterparts.

One-Pot, High-Yield Synthesis of Convex Au Octahedra by H2O2 - Mediated Process In Solution Phase

A simple, non-seeding and high-yield synthesis of convex gold octahedra with size of ca. 50 nm in aqueous solution is described. The octahedral nanoparticles were systematically prepared by reduction of HAuCl4 using ascorbic acid (AA) in the presence of cetyltrimethylammonium bromide (CTAB) as the stabilizing surfactant while concentrations of Au3+ were fixed. The synthesizing process is especially different to other wet synthesis of metallic nanoparticles because it is mediated by H2O2. Mechanism of the H2O2 – mediated process will be described in details. The gold octahedra were shown to be single crystals with all 8 faces belonging to {111} family. Moreover, the single crystalline particles also showed attractive optical properties towards LSPR that should find uses as labels for microscopic imaging, materials for colorimetric biosensings, or nanosensor developments.

Epitaxial BiFeO3 nanostructures fabricated by differential etching of BiFeO3 films

We report on differential etching behavior of the different orientations of the polarization in BiFeO3 (BFO), similar to other ferroelectrics, such as LiNbO3. We show how this effect can be used to fabricate epitaxial BiFeO3 nanostructures. By means of piezoresponse force microscopy (PFM) domains of arbitrary shape and size can be poled in an epitaxial BiFeO3 film, which are then reproduced in the film morphology by differential etching. Structures with a lateral size smaller than 200 nm were fabricated and very good retention properties as well as a highly increased piezoelectric response were detected by PFM. (C) 2011 American Institute of Physics. [doi:10.1063/1.3630027]