Development of a ReaxFF reactive force field for ettringite and study of its mechanical failure modes from reactive dynamics simulations

Ettringite is a hexacalcium aluminate trisulfate hydrate mineral that forms during Portland cement hydration. Its presence plays an important role in controlling the setting rate of the highly reactive aluminate phases in cement paste and has also been associated with severe cracking in cured hardened cement. To understand how it forms and how its properties influence those of hardened cement and concrete, we have developed a first-principles-based ReaxFF reactive force field for Ca/Al/H/O/S. Here, we report on the development of this ReaxFF force field and on its validation and application using reactive molecular dynamics (RMD) simulations to characterize and understand the elastic, plastic, and failure response of ettringite at the atomic scale. The ReaxFF force field was validated by comparing the lattice parameters, pairwise distribution functions, and elastic constants of an ettringite crystal model obtained from RMD simulations with those from experiments. The predicted results are in close agreement with published experimental data. To characterize the atomistic failure modes of ettringite, we performed stress-strain simulations to find that Ca-O bonds are responsible for failure of the calcium sulfate and tricalcium aluminate (C3A) column in ettringite during uniaxial compression and tension and that hydrogen bond re-formation during compression induces an increase in plastic strain beyond the material's stress-strain proportionality limit. These results provide essential insight into understanding the mechanistic role of this mineral in cement and concrete degradation, and the ReaxFF potential developed in this work serves as a fundamental tool to further study the kinetics of hydration in cement and concrete.     

Reductive Ring Opening of Ephedrine and Pseudo-Ephedrine-Derived Oxazolidinium Methiodides by Sodium Borohydride. A Direct Access to New Chiral Amine-Borane Adducts

Sodiun borohydride reacts with oxazolidinium methiodides derived from ephedrine and pseudoephedrine, in ethereal solvents, cleaving regioselectively the C-N bond of the ring and leading, in good yields, to chiral amine-borane adducts of know absolute configuration. The ¹HNMR data allow to predict the most stable conformation.     

Identification of markers of thermal processing (“roasting”) in aqueous extracts of Coffea arabica L. seeds through NMR fingerprinting and chemometrics

Roasting of Coffea arabica L. seeds gives rise to chemical reactions that produce more than 800 compounds, some being responsible for the desired organoleptic properties for which the beverage called “coffee” is known. In the industry, the “roasting profile,” that is, the times and temperatures applied, is key to influence the composition of roasted coffee beans and the flavour of the beverage made from them. The impact of roasting on the chemical composition of coffee has been the subject of numerous studies, including by nuclear magnetic resonance (NMR) spectroscopy. However, the roasting equipment and profiles applied in these studies are often far from real industrial conditions. In this work, the effects of two critical technological parameters of the roasting process, namely, the “development time” (the period of time after the “first crack,” a characteristic noise due to seed disruption) and the final roasting temperature on coffee extracts, were investigated. Seeds were roasted at pilot scale according to 13 industrial roasting profiles and extracted in D₂O. The extracts were analysed by ¹H NMR experiments. The NMR spectra were compared using (a) quantitative analysis of main signals by successive orders of magnitude and (b) chemometric tools (principal component analysis, partial least squares and sparse-orthogonal partial least squares analysis). This allowed to identify compounds, which may serve as markers of roasting and showed that changes in chemical composition can be detected even for slight change in final temperature (~1°C) or in total roasting time (~25 s).     

Adsorption of noble gases on metal surfaces and the scanning tunneling microscope

Physisorption on metal surfaces, and the tunneling currents through the adsorbed species, are calculated using a unified formalism that presents both problems on the same footing. Our method is based on a self-consistent LCAO approach whereby the different interaction parameters defining the bonds, and the tunneling currents, are calculated using the atomic properties of the atomic species forming the interface. Green function methods and the Keldish formalism are used to calculate the different physical properties. We present results for xenon adsorbed on aluminum.     

Efficient synthesis of [3H]-sanglifehrin A via selective oxidation/reduction of alcohols at C31 and C35

[Reaction: see text]. Sanglifehrin A is a novel complex natural product showing strong immunosuppressive activity and remarkably high affinity for cyclophilin A. To assess its pharmacokinetic properties in vivo, an efficient synthetic route was developed to introduce a tritium label in position C35 of sangliferin A via an oxidation/reduction strategy. The synthetic approach is particularly attractive, because the C35-oxo intermediate 7 is available in good yield on large scale and the reducing agent, lithium tri-sec-butylborotritide, is readily available. An attempt to apply a similar strategy to the alcohol in position C31 led primarily to C31-epi-hydroxy sanglifehrin A under a variety of conditions.     

New adsorbents from oil shales: Preparation, characterization and U, Th isotope adsorption tests

New activated adsorbents for radionuclides have been produced from Moroccan oil shales by pyrolysis of the natural material at 550 °C flowed by a KMnO₄ activation. The texture and composition of the native rock and the adsorbents were studied before their use in tests for adsorption of radionuclides from standard solutions prepared from uranylnitrate and thorium nitrate in equilibrium with their daughters. The distribution coefficients between solutions containing U, Th and Ra and the adsorbents were evaluated by means of specific activities, measured by g-ray spectrometry. The adsorbents were observed to eliminate U, Th, Ra, Ac and Tl from aqueous solutions. This revised version was published online in August 2006 with corrections to the Cover Date.     

Design and synthesis of a transferable farnesyl pyrophosphate analogue to Ras by protein farnesyltransferase

The posttranslational addition of a farnesyl moiety to the Ras oncoprotein is essential for its membrane localization and is required for both its biological activity and ability to induce malignant transformation. We describe the design and synthesis of a farnesyl pyrophosphate (FPP) analogue, 8-anilinogeranyl pyrophosphate 3 (AGPP), in which the omega-terminal isoprene unit of the farnesyl group has been replaced with an aniline functionality. The key steps in the synthesis are the reductive amination of the alpha,beta-unsaturated aldehyde 5 to form the lipid analogue 6, and the subsequent conversion of the allylic alcohol 7 to the chloride 8 via Ph(3)PCl(2) followed by displacement with [(n-Bu)(4)N](3)HP(2)O(7) to give AGPP (3). AGPP is a substrate for protein farnesyltransferase (FTase) and is transferred to Ras by FTase with the same kinetics as the natural substrate, FPP. AGPP is highly selective, showing little inhibitory activity against either geranylgeranyl-protein transferase type I (GGTase I) (K(i) = 0.06 microM, IC(50) = 20 microM) or squalene synthase (IC(50) = 1000 microM). AGPP is the first efficiently transferable analogue of FPP to be modified at the omega-terminus that provides a platform from which additional analogues can be made to probe the biological function of protein farnesylation. AGPP is the first example of a class of compounds that are alternate substrates for protein isoprenylation that are not inhibitors of squalene synthase.     

H2O nucleation around Au+

First principles electronic structure calculations have been carried out to investigate the ground state geometry, electronic structure, and the binding energy of [Au(H2O)n]+ clusters containing up to 10 H2O molecules. It is shown that the first coordination shell of Au+ contains two H2O molecules forming a H2O-Au+-H2O structure with C2 symmetry. Subsequent H2O molecules bind to the previous H2O molecules forming stable and fairly rigid rings, each composed of 4 H2O molecules, and leading to a dumbbell structure at [Au(H2O)8]+. The 9th and the 10th H2O molecules occupy locations above the Au+ cation mainly bonded to one H2O from each ring, leading to structures where the side rings are partially distorted and forming structures that resemble droplet formation around the Au+ cation. The investigations highlight quantum effects in nucleation at small sizes and provide a microscopic understanding of the observed incremental binding energy deduced from collision induced dissociation that indicates that [Au(H2O)n]+ clusters with 7-10 H2O molecules have comparable binding energy. The charge on the Au+ is shown to migrate to the outside H2O molecules, suggesting an interesting screening phenomenon.     

DNA-based phosphane ligands

In order to expand the repertoire of DNA sequences specifically interacting with transition metals, we report here the first examples of DNA sequences carrying mono- and bidentate phosphane ligands as well as P,N-ligands. Aminoalkyl-modified oligonucleotides have been reacted at predetermined internal sites with carboxylate derivatives of pyrphos, BINAP and phosphinooxazoline (PHOX) 2 b-d. Carbodiimide coupling in the presence of N-hydroxysuccinimide provided the DNA-ligand conjugates in 38-78 % yield. Phosphane-containing oligonucleotides and their phosphane sulfide analogues were characterized by mass spectrometry (MALDI-TOF and FT-ICR-ESI) and their stability after purification and isolation was systematically investigated. While DNA-appended pyrphos ligand was quickly oxidized, BINAP and PHOX conjugates showed high stabilities, making them useful precursors for incorporation of transition metals into DNA.