Pd–H and Ni–H phase diagrams using cluster variation method and Monte Carlo simulation

This work focuses on interstitial solid solutions of hydrogen in the face-centred cubic (fcc) host lattice of palladium and nickel, using a first-principles based approach. Cluster Variation Method (CVM) and Monte Carlo simulation algorithms were especially designed, allowing a coupled use of both techniques, to study hydrogen–vacancy interactions inside an fcc metallic host lattice. First-principles calculations provided the H–Vac interaction energies by structure inversion method. The phase diagrams and thermodynamic properties were computed using only theoretical inputs. The mechanisms leading to the formation of the miscibility gaps observed for both Pd–H and Ni–H systems and the hydrogen ordering on palladium interstitial lattice were reproduced without any empirical term.     

Synthesis and anti-HIV activity of 5-haloethynyl and 5-(1,2-dihalo)vinyl analogues of AZT and FLT

In this paper, we report the synthesis of hitherto unknown 5-haloethynyl and 5-(1,2-dihalo)vinyluracil nucleoside analogues of the anti-HIV AZT, and FLT drugs. The key step of those syntheses is a Pd(0) cross-coupling at C5 position under Sonogashira conditions. Finally, based on their in vitro anti-HIV activities and their cytotoxicity on PBM, CEM, and VERO cell lines, the best compounds were the 2′,3′-dideoxy-3′-fluoro-5-(bromo-2-iodo)vinyluridine (10b, EC₅₀ of 0.6 μM), and the 3′-azido-2′,3′-dideoxy-5-(bromo-2-iodo)vinyluridine (16b, EC₅₀ of 1.1 μM).     

Q-branch linewidths of N2 perturbed by H2: experiments and quantum calculations from an ab initio potential

In this work the authors present an experimental and theoretical study about the Q-branch lines' broadening coefficients of N2 perturbed by H2. Experimental values for these parameters have been obtained at 440 and 580 K, and quantum calculations have been performed using a new ab initio potential energy surface, obtained by quantum chemistry methods. The results of these calculations are compared to experimental data obtained previously at 77 and 298 K [L. Gomez et al., Mol. Phys. 104, 1869 (2006)] and to the present measurements. A satisfactory agreement is obtained for the whole range of temperatures used in the experiments.     

Precise mass measurement of a double-stranded 500 base-pair (309 kDa) polymerase chain reaction product by negative ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS) has been used to determine the mass of a double-stranded 500 base-pair (bp) polymerase chain reaction (PCR) product with an average theoretical mass of the blunt-ended (i.e. unadenylated) species of 308 859.35 Da. The PCR product was generated from the linearized bacteriophage Lambda genome which is a double-stranded template. Utilization of ethanol precipitation in tandem with a rapid microdialysis step to purify and desalt the PCR product was crucial to obtain a precise mass measurement. The PCR product (0.8 pmol/μL) was electrosprayed from a solution containing 75% acetonitrile, 25 mM piperidine, and 25 mM imidazole and was infused at a rate of 200 nL/min. The average molecular mass and the corresponding precision were determined using the charge-states ranging from 172 to 235 net negative charges. The experimental mass and corresponding precision (reported as the 95% confidence interval of the mean) was 309 406 +/- 27 Da (87 ppm). The mass accuracy was compromised due to the fact that the PCR generates multiple products when using Taq polymerase due to the non-template directed 3'-adenylation. This results in a mixture of three PCR products with nearly identical mass (i.e. blunt-ended, mono-adenylated and di-adenylated) with unknown relative abundances that were not resolved in the spectrum. Thus, the experimental mass will be a weighted average of the three species which, under our experimental conditions, reflects a nearly equal concentration of the mono- and di-adenylated species. This report demonstrates that precise mass measurements of PCR products up to 309 kDa (500 bp) can be routinely obtained by ESI-FTICR requiring low femtomole amounts. Copyright 1999 John Wiley & Sons, Ltd.     

Translational and rotational invariance requisites for density functional derivatives

Translational and rotational invariance of functionals lead to hierarchies of equations between successive derivatives. These hierarchies allow alternating series expansions of some density functionals in terms of functional derivatives and charge density. Translational and rotational invariance also give rise to integrodifferential equations that link derivatives of all orders. From the minimal properties of the kinetic energy functional T_s[ρ] and the functional F[ρ] = min_Ψ→ρ <Ψ|T + V_ee|Ψ>, it follows that $int dˆ3 r dˆ3 rˆprimef({bold r}) {delˆ2 T―s[rho]}over{delrho({bold r})delrho({bold rˆprime})}f({bold rˆprime}) geq 0hspace{1cm}hbox{and}hspace{1cm}int dˆ3 r dˆ3 rˆprimef({bold r}) {delˆ2 F[rho]}over{delrho({bold r})delrho({bold rˆprime})}f({bold rˆprime}) geq 0$ for all ∫ d³ r d³ f′ f(r) = 0. This property combined with constraints on functionals due to translational invariance lead to inequalities satisfied by first derivatives of selected density functionals. © 1997 John Wiley & Sons, Inc.     

Improving the Performance of a Continuous Process for the Production of Ethanol from Starch

In a previous work, a continuous simultaneous saccharification and fermentation process to produce ethanol from cassava starch was studied, using a set of fixed-bed reactors. The biocatalyst consisted of glucoamylase immobilized in silica particles and co-immobilized with S. cerevisiae in pectin gel. Using 3.8 U mL^?1 _reactor and 0.05 g_{wet yeast} mL^?1 _reactor at start-up, starch hydrolysis was the rate-limiting step. Maximum ethanol productivity was 5.8 g_ethanol L^?1 h^?1, with 94.0% conversion of total reducing sugars (TRS) and 83.0% of the ethanol theoretical yield. In this work, the molar mass of the substrate and the biocatalyst particle size were reduced in an attempt to improve the bioreactor performance. The diameters of silica and pectin gel particles were reduced from 100 μm and 3–4 mm, respectively, to 60 μm and 1–1.5 mm, and the degree of substrate prehydrolysis by α-amylase was increased. The bioreactor performance was assessed for different loads of immobilized glucoamylase (2.1, 2.8, and 3.8 U mL^?1 _reactor), for the same initial cell concentration (0.05 g_{wet yeast.}mL^?1 _reactor). Feeding with 154.0 g L^?1 of TRS and using 3.8 U mL^?1 _reactor, fermentation became the rate-limiting step. Productivity reached 11.7 g L^?1 h^?1, with 97.0% of TRS conversion and 92.0% of the ethanol theoretical yield. The reactor was operated during 275 h without any indication of destabilization.     

Synthesis of (±)-1,2,3-triazolo-3′-deoxy-4′-hydroxymethyl carbanucleosides via ‘click’ cycloaddition

The synthesis of 1,2,3-triazolo-3′-deoxy-4′-hydroxymethyl carbanucleosides with different reaction conditions and diverse modulations on the heterocycle residues was developed. Heterocycle moieties were efficiently introduced on the pseudo-sugar either via nucleophilic substitution or via 1,3-dipolar Huisgen cycloaddition. With this latter approach, 1,4-disubstituted and 1,4,5-trisubstituted-(±)-[1,2,3]-triazolo-3′-deoxy-4′-hydroxymethyl carbanucleosides were prepared from the corresponding azido-carbocycle and various terminal or internal alkynes. Antiviral activities and cellular toxicities of the final compounds were evaluated as smallpox inhibitors. Unfortunately, at concentrations up to 100 mM, none of them inhibited production of vaccinia virus (Lister strain) or cowpox virus (Brighton strain) in vero cells.     

Ab initio study of phonon dispersion and thermodynamic properties of pure and doped pyrites

Pyrites (FeS₂) are solid minerals that are found abundantly in Nigeria and are easy to prepare in laboratories. In this work, FeS₂ is studied extensively in its pure state as well as when iron is substitutionally doped with zinc and calcium at concentrations of 0, 0.25, 0.5, 0.75 and 1. Using density functional theory, the eectronic, dynamic and thermodynamic properties were calculated. The results revealed that the lattice parameters and bulk modulus increases with increasing concentration and the obtained values are in agreement with available experimental and theoretical values. Though pyrite, when doped with zinc, obeys Vegard’s law, doping with calcium revealed pronounced deviation from this law. The calculated band structures showed that FeS₂ has an indirect band gap whose size decreases after introducing zinc while doping with calcium increases the band gap. The phonon dispersion of the end members FeS₂ and ZnS₂ indicate that the systems are dynamically stable while CaS₂ is dynamically unstate. Also, the thermodynamic properties of the pure and doped pyrites were calculated and the ranges of temperature at which the lattice and electronic degrees of freedom contribute to the specific heat capacity are presented.