Complexes formed between nitrilotris(methylenephosphonic acid) and M(2+) transition metals: isostructural organic-inorganic hybrids

Nitrilotris(methylenephosphonic acid) (NTP, [N(CH(2)PO(3)H(2))(3)]) recently has been found to form three-dimensional porous structures with encapsulation of templates as well as layered and linear structures with template intercalation. It was, therefore, of interest to examine the type of organic-inorganic hybrids that would form with metal cations. Mn(II) was found to replace two of the six acid protons, while a third proton bonds to the nitrilo nitrogen, forming a zwitter ion. Two types of compounds were obtained. When the ratio of acid to Mn(II) was less than 10, a trihydrate, Mn[HN(CH(2)PO(3)H)(3)(H(2)O)(3)] (2) formed. Compound 2 is monoclinic P2(1)/c, with a = 9.283(2) A, b = 16.027(3) A, c = 9.7742(2) A, beta = 115.209(3) degrees, V = 1315.0(5) A(3), and Z = 4. The Mn atoms form zigzag chains bridged by two of the three phosphonate groups. The third phosphonate group is only involved in hydrogen bonding. The metal atoms are octahedrally coordinated with three of the sites occupied by water molecules. Adjacent chains are hydrogen-bonded to each other through POH and HN donors, and the additional participation of all the water hydrogens in H-bonding results in a corrugated sheet-like structure. Use of excess NTP at a ratio to metal of 10 to 1 yields an anhydrous compound Mn[HN(CH(2)PO(3)H)(3)] (1), P2(1)/n, a = 9.129(1) A, b = 8.408(1) A, c = 13.453(1) A, beta = 97.830(2) degrees, V = 1023.0(2) A(3), and Z = 4. Manganese is five coordinate forming a distorted square pyramid with oxygens from five different phosphonate groups. The sixth oxygen is 2.85 A from an adjacent Mn, preventing octahedral coordination. All the protonated atoms, three phosphonate oxygens and N, form moderately strong hydrogen bonds in a compact three-dimensional structure. The open-structured trihydrate forms a series of isostructural compounds with other divalent transition metal ions as well as with mixed-metal compositions. This is indicative that the hydrogen bonding controls the type of structure formed irrespective of the cation.     

Domino metathesis of 2-azanorbornenones: a new strategy for the enatioselective synthesis of 1-azabicyclic compounds

Domino metathesis of N-alkylated derivatives of (1S)-2-azanorborn-5-en-3-one allowed for the enantioselective synthesis of pyrrolizidine, quinolizidine, pyrrolidinoazepine, and pyrrolidinoazocine derivatives in a straightforward process.     

Design of ordered bimetallic complexes,Part 2:Trans-1,2-cyclohexanediaminetetraacetate bimetallates

Summary Knowledge of the kinetic and thermodynamic behaviour of aqueous solutions containing two divalent cations andtrans-1,2-cyclohexanediaminetetraacetate has been used to design synthetic pathways to ordered bimetallic complexesPart 1: E. Escriva, A. Fuertes and D. Beltran,Transition Met. Chem.,9, 184 (1984).     

Structure Determination of a Complex Tubular Uranyl Phenylphosphonate, (UO(2))(3)(HO(3)PC(6)H(5))(2)(O(3)PC(6)H(5))(2).H(2)O, from Conventional X-ray Powder Diffraction Data

The three-dimensional structure of a complex tubular uranyl phosphonate, (UO(2))(3)(HO(3)PC(6)H(5))(2)(O(3)PC(6)H(5))(2).H(2)O, was determined ab initio from laboratory X-ray powder diffraction data and refined by the Rietveld method. The crystals belong to the space group P2(1)2(1)2(1), with a = 17.1966(2) ?, b = 7.2125(2) ?, c = 27.8282(4) ?, and Z = 4. The structure consists of three independent uranium atoms, among which two are seven-coordinated and the third is eight-coordinated. These metal atoms are connected by four different phosphonate groups to form a one-dimensional channel structure along the b axis. The phenyl groups are arranged on the outer periphery of the channels, and their stacking forces keep the channels intact in the lattice. The determination of this structure which contains 50 non-hydrogen atoms in the asymmetric unit, from conventional X-ray powder data, represents significant progress in the application of powder techniques to structure solution of complex inorganic compounds, including organometallic compounds.     

Synthetic Strategies To Obtain V-P-O Open Frameworks Containing Organic Species as Structural Directing Agents. Crystal Structure of the V(IV)-Fe(III) Bimetallic Phosphate [H(3)N(CH(2))(2)NH(3)](2)[H(3)N(CH(2))(2)NH(2)][Fe(III)(H(2)O)(2)(V(IV)O)(8)(OH)(4)(HPO(4))(4)(PO(4))(4)].4H(2)O

A general synthetic approach to rationalize the solution preparative chemistry of oxovanadium phosphates containing organic species as structural directing agents is presented. Careful attention is payed to the hydrolysis and condensation processes involving the ionic species in solution, and a simple restatement of the partial charge model (PCM) has been used in order to organize the experimental results. The structure of a new V(IV)-Fe(III) bimetallic oxovanadium phosphate, [H(3)N(CH(2))(2)NH(3)](2)[H(3)N(CH(2))(2)NH(2)] [Fe(III)(H(2)O)(2)(V(IV)O)(8)(OH)(4)(HPO(4))(4)(PO(4))(4)].4H(2)O, has been determined by X-ray single crystal diffraction methods. This compound crystallizes in the monoclinic system, space group P2(1)/n and the cell dimensions are as follows: a = 14.383(3) ?, b = 10.150(2) ?, c = 18.355(4) ?, and beta = 90.39(3) degrees (Z = 2). The existence of a complex intercrossing channel system, including a very large channel of 18.4 ? of diameter (in which both water molecules and ethylenediamine species are located), is the more interesting feature of this structure. Thermal decomposition, including the dehydration/rehydration process, has been studied by thermal analysis and variable temperature X-ray powder diffraction techniques. A complementary SEM study of the different intermediate decomposition products is presented.     

Synthesis and Biological Evaluation of RGD Peptidomimetic–Paclitaxel Conjugates Bearing Lysosomally Cleavable Linkers

Two small‐molecule–drug conjugates (SMDCs, 6 and 7 ) featuring lysosomally cleavable linkers (namely the Val–Ala and Phe–Lys peptide sequences) were synthesized by conjugation of the α_vβ₃‐integrin ligand cyclo[DKP–RGD]‐CH₂NH₂ ( 2 ) to the anticancer drug paclitaxel (PTX). A third cyclo[DKP–RGD]–PTX conjugate with a nonpeptide “uncleavable” linker ( 8 ) was also synthesized to be tested as a negative control. These three SMDCs were able to inhibit biotinylated vitronectin binding to the purified α_Vβ₃‐integrin receptor at nanomolar concentrations and showed good stability at pH 7.4 and pH 5.5. Cleavage of the two peptide linkers was observed in the presence of lysosomal enzymes, whereas conjugate 8 , which possesses a nonpeptide “uncleavable” linker, remained intact under these conditions. The antiproliferative activities of the conjugates were evaluated against two isogenic cell lines expressing the integrin receptor at different levels: the acute lymphoblastic leukemia cell line CCRF‐CEM (α_Vβ₃?) and its subclone CCRF‐CEM α_Vβ₃ (α_Vβ₃+). Fairly effective integrin targeting was displayed by the cyclo[DKP–RGD]–Val–Ala–PTX conjugate ( 6 ), which was found to differentially inhibit proliferation in antigen‐positive CCRF‐CEM α_Vβ₃ versus antigen‐negative isogenic CCRF‐CEM cells. The total lack of activity displayed by the “uncleavable” cyclo[DKP–RGD]–PTX conjugate ( 8 ) clearly demonstrates the importance of the peptide linker for achieving the selective release of the cytotoxic payload.     

Noise Reduction in Spur Gear Systems

This article lists some tips for reducing gear case noise. With this aim, a static analysis was carried out in order to describe how stresses resulting from meshing gears affect the acoustic emissions. Different parameters were taken into account, such as the friction, material, and lubrication, in order to validate ideas from the literature and to make several comparisons. Furthermore, a coupled Eulerian–Lagrangian (CEL) analysis was performed, which was an innovative way of evaluating the sound pressure level of the aforementioned gears. Different parameters were considered again, such as the friction, lubrication, material, and rotational speed, in order to make different research comparisons. The analytical results agreed with those in the literature, both for the static analysis and CEL analysis—for example, it was shown that changing the material from steel to ductile iron improved the gear noise, while increasing the rotational speed or the friction increased the acoustic emissions. Regarding the CEL analysis, air was considered a perfect gas, but its viscosity or another state equation could have also been taken into account. Therefore, the above allowed us to state that research into these scientific fields will bring about reliable results.