Synthesis, structure and properties of SrAu3In3 and EuAu3In3—New indides with gold zig-zag chains

New indides SrAu₃In₃ and EuAu₃In₃ were synthesized by induction melting of the elements in sealed tantalum tubes. Both indides were characterized by X-ray diffraction on powders and single crystals. They crystallize with a new orthorhombic structure type: Pmmn, Z=2, a=455.26(9), b=775.9(2), c=904.9(2) pm, wR2=0.0425, 485 F² values for SrAu₃In₃ and a=454.2(2), b=768.1(6), c=907.3(6) pm, wR2=0.0495, 551 F² values for EuAu₃In₃ with 26 variables for each refinement. The gold and indium atoms build up three-dimensional [Au₃In₃] polyanionic networks, which leave distorted hexagonal channels for the strontium and europium atoms. Within the networks one observes Au2 atoms without Au-Au contacts and gold zig-zag chains (279 pm Au1-Au1 in EuAu₃In₃). The Au-In and In-In distances in EuAu₃In₃ range from 270 to 290 and from 305 to 355 pm. The europium atoms within the distorted hexagonal channels have coordination number 14 (8 Au+6 In). EuAu₃In₃ shows Curie-Weiss behavior above 50 K with an experimental magnetic moment of 8.1(1) μB/Eu atom. ¹⁵¹Eu Mössbauer spectra show a single signal at δ=−11.31(1) mm/s, compatible with divalent europium. No magnetic ordering was detected down to 3 K.     

Development of Novel Pyridine-Thiazole Hybrid Molecules as Potential Anticancer Agents

Novel pyridine-thiazole hybrid molecules were synthesized and subjected to physico-chemical characterization and screening of their cytotoxic action towards a panel of cell lines derived from different types of tumors (carcinomas of colon, breast, and lung, glioblastoma and leukemia), and normal human keratinocytes, for comparison. High antiproliferative activity of the 3-(2-fluorophenyl)-1-[4-methyl-2-(pyridin-2-ylamino)-thiazol-5-yl]-propenone 3 and 4-(2-{1-(2-fluorophenyl)-3-[4-methyl-2-(pyridin-2-ylamino)-thiazol-5-yl]-3-oxopropylsulfanyl}-acetylamino)-benzoic acid ethyl ester 4 was revealed. The IC₅₀ of the compound 3 in HL-60 cells of the acute human promyelocytic leukemia was 0.57 µM, while in the pseudo-normal human cell lines, the IC₅₀ of this compound was >50 µM, which suggests that the compounds 3 and 4 might be perspective anticancer agents. The detected selectivity of the derivatives 3 and 4 for cancer cell lines inspired us to study the mechanisms of their cytotoxic action. It was shown that preincubation of tumor cells with Fluzaparib (inhibitor of PARP1) reduced the cytotoxic activity of the derivatives 3 and 4 by more than twice. The ability of these compounds to affect DNA nativity and cause changes in nucleus morphology allows for the suggestion that the mechanism of action of the novel pyridine-thiazole derivatives might be related to inducing the genetic instability in tumor cells.     

Ca3Ni8In4—An Ordered Noncentrosymmetric Variant of the BaLi4 Type

The title compound was synthesized by reacting the elements in an arc-melting apparatus under purified argon and subsequent annealing at 870 K. Ca₃Ni₈In₄ was investigated using X-ray diffraction on both powders and single crystals: P6₃mc, a=898.9(1) pm, c=752.2(2) pm, wR2=0.0591, 327 F² values, and 35 parameters. This structure is an ordered, noncentrosymmetric variant of the BaLi₄ type. The nickel and indium atoms build a complex three-dimensional [Ni₈In₄] polyanion in which the calcium atoms fill distorted hexagonal channels. To a first approximation the formula may be written as (3 Ca²⁺)⁶⁺ [Ni₈In₄]⁶⁻. Within the polyanion the Ni1, Ni3, and Ni4 atoms form one-dimensional cluster units which extend in the c direction while the Ni2 atoms have only indium neighbors in a distorted tetrahedral coordination. The Ni–Ni distances in the cluster range from 241 to 266 pm. The cluster units are surrounded and interconnected by indium atoms. The group– subgroup relation from centrosymmetric BaLi₄ to noncentrosymmetric Ca₃Ni₈In₄ is presented. Chemical bonding in Ca₃Ni₈In₄ and the structural relation with Lu₃Co_7.77Sn₄, Ca₃Au_6.61Ga_4.39, and Co₂Al₅ is briefly discussed.     

Gd-doping of HfO2

An increase in the density of states between the oxygen 2p bands and the Fermi level is seen with increasing Gd concentrations. In addition, for the Gd-doped HfO₂ films, the Gd 4f photoexcitation peak at 5.5 eV below the valence band maximum was identified using resonant photoemission. Electrical measurements show pronounced rectification properties for lightly-doped Gd:HfO₂ films on p-Si and for heavily-doped Gd:HfO₂ films on n-Si, suggesting a crossover from n-type to p-type behavior with increasing doping level. In addition, there is an increase in the reverse bias current with neutron irradiation.     

Negative magnetoresistance in Cr-containing diamond-like carbon-based heterostructures

We have characterized the local structure around the Cr atom, as a function of Cr content, in films of chromium-doped hydrogenated amorphous diamond-like carbon (Cr-DLC) synthesized by plasma-enhanced chemical vapor deposition (PECVD). The composition appears to be related to the structure and forward bias magnetoresistance in heterojunction devices. Chromium in diamond-like carbon (DLC) has a chemical state much like chromium carbide and, at low Cr content, the Cr is dissolved in an amorphous DLC matrix forming an atomic-scale composite. At higher Cr content, Cr is present as nano-composite and chromium carbide precipitates preferentially form at the surface of the film. In these films of higher chromium concentration, a large coefficient of negative magnetoresistance is observed in heterojunction devices with n-type silicon.     

Bi-Poisson Structures and Integrability of Geodesic Flow on Homogeneous Spaces

Let G/K be a semisimple orbit of the adjoint representation of a real connected reductive Lie group G. Let K₁ be any closed subgroup of K containing the commutant of the identity component of K. We prove that the geodesic flow on the symplectic manifold T*(G/K₁), corresponding to a G-invariant pseudo-Riemannian metric on G/K₁ which is induced by a bi-invariant pseudo-Riemannian metric on G, is completely integrable in the class of real analytic functions, polynomial in momenta. To this end we study the Poisson geometry of the space of G-invariant functions on T*(G/K) using a one-parameter family of moment maps.     

A total synthesis of (±)-dihydropalustrine

Dihydropalustrine has been synthesized by a β-lactam-imino ether coupling route. A dehydro precursor previously considered to represent palustrine has now been shown to be nonidentical with the natural product.     

Infinite Gold Zig‐Zag Chains as Structural Motif in Ca3Au3In – A Ternary Ordered Variant of the Ni4B3 Type

New auride Ca₃Au₃In was synthesized from the elements in a sealed tantalum tube in a high‐frequency furnace. Ca₃Au₃In was investigated by X‐ray powder and single crystal diffraction: ordered Ni₄B₃ type, Pnma, a = 1664.1(6), b = 457.3(2), c = 895.0(3) pm, wR2 = 0.0488, 1361 F² values, and 44 variables. The three crystallographically independent boron positions of the Ni₄B₃ type are occupied by the gold atoms, while the four nickel sites are occupied by calcium and indium in an ordered manner. All gold atoms have trigonal prismatic coordination, i.e. Ca₆ prisms for Au1 and Au2 and Ca₄In₂ prisms for Au3. While the Au3 atoms are isolated, we observe Au1–Au1 and Au2–Au2 zig‐zag chains at Au–Au distances of 292 and 284 pm. These slabs resemble the CrB type structure of CaAu. Consequently Ca₃Au₃In can be considered as a ternary auride. Together the Au2, Au3 and indium atoms build up a three‐dimensional [Au₂In] polyanionic network (281–293 pm Au–In) in which the chains of Au1 centered trigonal prisms are embedded. The crystal chemical similarities with the structures of Ni₄B₃, CaAuIn, and CaAu are discussed.     

Nonwettable thin films from hybrid polymer brushes can be hydrophilic

Hybrid brushes composed of two liquid polymers, poly(dimethylsiloxane) (PDMS) and a highly branched ethoxylated polyethylenimine (EPEI), were synthesized on Si wafers by the "grafting to" method and by applying a combinatorial approach (fabrication of gradient brushes). The combinatorial approach revealed a strong effect of "layer assisted tethering", which allowed us to synthesize hybrid brushes twice as thick as the reference homopolymer brushes. The hybrid brushes are stable thin films that can rapidly and reversibly switch between hydrophilic and hydrophobic states in water and air, respectively. The switching in water affects a rapid release of amino functional groups which can be used to regulate adhesion and reactivity of the material. The switching in air rapidly returns the brush to a hydrophobic state. The hybrid brush is hydrophilic because of two mechanisms: (1) exposure of EPEI chains to the brush-water interface under water, and (2) retention of some fraction of water via swollen EPEI chains (the EPEI chains swell by 2-3 times), which are conserved by a PDMS cap in air. The hybrid brush is wettable under water, and at the same time, the brush is nonwettable in air because water droplets are trapped in a metastable state when the water contact angle is above 90 degrees .