Search Results (4)

Zero valent iron (Fe⁰) water remediation studies, over the last 40 years, have periodically reported the discovery of C_nH_2n+2 in the product water or product gas, where n = 1 to 20. Various theories have been proposed for the presence of these hydrocarbons. These include: (i) reductive transformation of a more complex organic chemical; (ii) hydrogenation of an organic chemical, as part of a degradation process; (iii) catalytic hydrogenation and polymerisation of carbonic acid; and (iv) redox transformation. This study uses wastewater (pyroligneous acid, (pH = 0.5 to 4.5)) from a carbonization reactor processing municipal waste to define the controls for the formation of C_nH_2n+2 (where n = 3 to 9), C₃H₄, and C₃H₆. A sealed, static diffusion, batch flow reactor, containing zero-valent metals [181 g m-Fe⁰ + 29 g m-Al⁰ + 27 g m-Cu⁰ + 40 g NaCl] L⁻¹, was operated at two temperatures, 273–298 K and 348 K, respectively. The reactions, reactant quotients, and rate constants for the catalytic formation of H_2(g), CO_2(g), C₃H_4(g), C₃H_6(g), C₃H_8(g), C₄H_10(g), C₅H_12(g), C₆H_14(g,l), and C₇H_16(g,l), are defined as function of zero valent metal concentration (g L⁻¹), reactor pressure (MPa), and reactor temperature (K). The produced fuel gas (422–1050 kJ mole⁻¹) contained hydrogen + C_nH_y(gas), where n = 3 to 7. The gas production rate was: [1058 moles C_nH_y + 132 moles H₂] m⁻³ liquid d⁻¹ (operating pressure = 0.1 MPa; temperature = 348 K). Increasing the operating pressure to 1 MPa increased the fuel gas production rate to [2208 moles C_nH_y + 1071 moles H₂] m⁻³ liquid d⁻¹. In order to achieve these results, the Fe⁰, operated as a “Smart Material”, simultaneously multi-tasking to create self-assembly, auto-activated catalysts for hydrogen production, hydrocarbon formation, and organic chemical degradation (degrading carboxylic acids and phenolic species to CO₂ and CO). Full article

Here, the hierarchical assembly of a collagen mimetic peptide (CMP) displaying four bipyridine moieties is described. The CMP was capable of forming triple helices followed by self-assembly into disks and domes. Treatment of these disks and domes with metal ions such as Fe(II), Cu(II), Zn(II), Co(II), and Ru(III) triggered the formation of microcages, and micron-sized cup-like structures. Mechanistic studies suggest that the formation of the microcages proceeds from the disks and domes in a metal-dependent fashion. Fluorescently-labeled dextrans were encapsulated within the cages and displayed a time-dependent release using thermal conditions. Full article

The reaction of 2,6-diformyl-4-methylphenol (DFMF) with 1-amino-2-propanol (AP) and tris(hydroxymethyl)aminomethane (THMAM) was investigated in the presence of Cobalt(II) salts, (X = ClO₄⁻, CH₃CO₂⁻, Cl⁻, NO₃⁻), sodium azide (NaN₃), and triethylamine (TEA). In one pot, the variation in Cobalt(II) salt results in the self-assembly of dinuclear, tetranuclear, and H-bonding-directed polynuclear coordination complexes of Cobalt(III), Cobalt(II), and mixed-valence Co^IICo^III: [Co₂^III(H₂L⁻¹)₂(AP⁻¹)(N₃)](ClO₄)₂ (1), [Co₄(H₂L⁻¹)₂(µ₃-1,1,1-N₃)₂(µ-1,1-N₃)₂Cl₂(CH₃OH)₂]·4CH₃OH (2), [Co₂^IICo₂^III(HL⁻²)₂(µ-CH₃CO₂)₂(µ₃-OH)₂](NO₃)₂·2CH₃CH₂OH (3), and [Co₂^IICo₂^III (H₂L1²⁻)₂(THMAM⁻¹)₂](NO₃)₄ (4). In 1, two cobalt(III) ions are connected via three single atom bridges; two from deprotonated ethanolic oxygen atoms in the side arms of the ligands and one from the1-amino-2-propanol moiety forming a dinuclear unit with a very short (2.5430(11) Å) Co-Co intermetallic separation with a coordination number of 7, a rare feature for cobalt(III). In 2, two cobalt(II) ions in a dinuclear unit are bridged through phenoxide O and μ₃-1,1,1-N₃ azido bridges, and the two dinuclear units are interconnected by two μ-1,1-N₃ and two μ₃-1,1,1-N₃ azido bridges generating tetranuclear cationic [Co₄(H₂L⁻¹)₂(µ₃-1,1,1-N₃)₂(µ-1,1-N₃)₂Cl₂(CH₃OH)₂]²⁺ units with an incomplete double cubane core, which grow into polynuclear 1D-single chains along the a-axis through H-bonding. In 3, HL²⁻ holds mixed-valent Co(II)/Co(III) ions in a dinuclear unit bridged via phenoxide O, μ-1,3-CH₃CO₂⁻, and μ₃-OH⁻ bridges, and the dinuclear units are interconnected through two deprotonated ethanolic O in the side arms of the ligands and two μ₃-OH⁻ bridges generating cationic tetranuclear [Co₂^IICo₂^III(HL⁻²)₂(µ-CH₃CO₂)₂(µ_3-OH)₂]²⁺ units with an incomplete double cubane core. In 4, H₂L1⁻² holds mixed-valent Co(II)/Co(III) ions in dinuclear units which dimerize through two ethanolic O (μ-RO⁻) in the side arms of the ligands and two ethanolic O (μ₃-RO⁻) of THMAM bridges producing centrosymmetric cationic tetranuclear [Co₂^IICo₂^III (H₂L1⁻²)₂(THMAM⁻¹)₂]⁴⁺ units which grow into 2D-sheets along the bc-axis through a network of H-bonding. Bulk magnetization measurements on 2 demonstrate that the magnetic interactions are completely dominated by an overall ferromagnetic coupling occurring between Co(II) ions. Full article

We propose that the first step in the origin of cellular life on Earth was the self-assembly of fatty acids with the building blocks of RNA and protein, resulting in a stable aggregate. This scheme provides explanations for the selection and concentration of the prebiotic components of cells; the stabilization and growth of early membranes; the catalysis of biopolymer synthesis; and the co-localization of membranes, RNA and protein. In this article, we review the evidence and rationale for the formation of the proposed aggregate: (i) the well-established phenomenon of self-assembly of fatty acids to form vesicles; (ii) our published evidence that nucleobases and sugars bind to and stabilize such vesicles; and (iii) the reasons why amino acids likely do so as well. We then explain how the conformational constraints and altered chemical environment due to binding of the components to the membrane could facilitate the formation of nucleosides, oligonucleotides and peptides. We conclude by discussing how the resulting oligomers, even if short and random, could have increased vesicle stability and growth more than their building blocks did, and how competition among these vesicles could have led to longer polymers with complex functions. Full article