Prebiotic synthesis of sequential peptides on the Hadean beach by a molecular engine working with nitrogen oxides as energy sources

Addressing the still open question of the prebiotic origin of sequential macromolecules (peptides, nucleic acids) on the primitive Earth, we describe a molecular engine (the primary pump), which works at ambient temperature and continuously generates, elongates and complexifies sequential peptides. This new scenario is based on a cyclic reaction sequence, whose keystep is the activation of amino acids into their N‐carboxyanhydrides (NCA) through nitrosation by NOx. This process could have taken place on tidal beaches; it requires a buffered ocean, emerged land and a nitrosating atmosphere. With the help of geochemical studies and computer simulations of atmosphere photochemistry, we show that the primitive Earth during the Hadean may have satisfied all these requirements. © 2001 Society of Chemical Industry.     

The influence of NaCl and CO2 on the atmospheric corrosion of magnesium alloy AZ91

The influence of NaCl and CO₂ on the atmospheric corrosion of magnesium alloy AZ91 is studied in the laboratory. Samples were exposed under carefully controlled air and flow conditions; the relative humidity was 95%, the temperature was 22.0°C and the concentration of CO₂ was < 1 ppm or 350 ppm. Different amounts of sodium chloride (0–70 μg/cm²) were added before exposure. The corrosion products were analyzed by gravimetry, ion chromatography, X‐ray diffraction and scanning electron microscopy. Mass gain and metal loss results are reported. The combination of high humidity and NaCl is very corrosive towards AZ91. However, the NaCl‐induced corrosion is inhibited by ambient concentrations of CO₂. Exposure in the absence of CO₂ gives rise to heavy pitting, with brucite, Mg(OH)₂, being the dominant corrosion product. In the presence of CO₂ a layer of hydrated magnesium hydroxy carbonate, Mg₅(CO₃)₄(OH)₂ · 5 H₂O forms. A tentative corrosion mechanism is presented that explains the behavior in the two environments.     

Synthesis and characterization of novel diimide–dinaphthols and resulting poly(urethane–imide)s

Novel diols containing imide groups were prepared via condensation of aromatic dianhydrides with 5‐amino‐1‐naphthol. The diimide–dinaphthols prepared were characterized by conventional methods and used to synthesize new poly(urethane–imide)s (PUIs). All the polymers were characterized and their physical properties, such as solubility, solution viscosity, thermal stability, and thermal behaviour were studied. The polymers obtained showed more thermal stability than typical polyurethanes because of the presence of the imide groups. Copyright © 2003 Society of Chemical Industry     

Homogenization of hardness distribution and distortion in high pressure gas quenching

Quenching with gases rather than oil or other liquid media has the advantages of reducing the risks concerning health and environment, while simultaneously homogenizing the quenching results and minimizing distortion due to a wide range of possible process parameter variations and the pure convective heat transfer. In this contribution, a coupled solution for increasing homogenization of quenching results within high pressure gas quenching will be presented. In the first stage, an experimental test facility was set up for flow investigations and in the second stage a numerical simulation model was generated. The numerical and experimental results of the flow through the chamber were compared for several boundary conditions. Finally, after complete verification of the simulation, the model may be used to assist in parameter variation for optimization of homogeneous high pressure gas quenching.     

A Practical Method to Derive Sample Temperature during Nonisothermal Coupled Thermogravimetry Analysis and Differential Scanning Calorimetry Experiments

Nonisothermal thermogravimetry differential scanning calorimetry (TG‐DSC) mounting is intensively used for the determination of kinetic parameters and reaction heat along the chemical transformation of a solid. Nevertheless, when tests are performed with heating rates as high as those encountered in industrial processes, e.g., several tens of K min^–1, there is great uncertainty in the knowledge of the exact sample temperature. In this work, a method to derive a simple mathematical expression is proposed and fully described in order to calculate the real sample temperature throughout a temperature‐ramped test on a commercial apparatus. The furnace temperature and the heat flow signals were used, together with the crucible specific heat and the heating rate. A number of validation tests were performed to derive similar reaction rates for a reference. First‐order kinetic reactions were presented and reconciled over a large range of heating rates from 3 to 50 K min^–1.     

Effect of polymerization conditions on o‐phenylenediamine and o‐phenetidine oxidative copolymers

A series of new o‐phenylenediamine (OPD)/o‐phenetidine (PHT) copolymers with partly phenazine‐like structures has been successfully synthesized at three polymerization temperatures by chemically oxidative polymerization in four different polymerization media. The molecular structures and properties of the resulting OPD/PHT polymers were investigated by IR, UV–vis and high‐resolution ¹H NMR spectroscopies, and DSC, in order to ascertain the effect of reaction temperature, comonomer ratio and acid medium. The copolymerization mechanism of OPD with PHT monomers has been proposed. It is found that the statistical OPD/PHT copolymer obtained at a temperature of 118 °C has a higher degree of polymerization than that obtained at 12–17 °C. The OPD content in the copolymers calculated from NMR spectroscopic analysis is higher than that in the feed OPD content, whereas the OPD content calculated from element analysis is slightly lower than the feed OPD content. It can be predicted that denitrogenation takes place in the OPD units during the polymerization process at OPD/PHT molar ratios of 90/10 and 100/0. These OPD/PHT copolymers exhibit a much better solubility than the OPD homopolymer, hence suggesting an incorporation of PHT units into the phenazine structure of the homopolymer. The thermal behavior of the copolymers was also studied. Copyright © 2004 Society of Chemical Industry