Measurement of temperature, density, and particle transport with localized dopants in wire-array Z pinches

Axially localized NaF dopants are coated onto Al cylindrical wire arrays in order to act as spectroscopic tracers in the stagnated z-pinch plasma. Non-local-thermodynamic-equilibrium kinetic models fit to Na K-shell lines provide an independent measurement of the density and temperature that is consistent with spectroscopic analysis of K-shell emissions from Al and an alloyed Mg dopant. Axial transport of the Na dopant is observed, enabling quantitative study of instabilities in dense z-pinch plasmas.     

Racemic and (+)-ethyl 2-acetamido-2-carboxy-5-oxohexanoate

Racemic ethyl 2-acetamido-2-carboxy-5-oxohexanoate has been isolated by single hydrolysis of the corresponding diethyl ester and resolved essentially quantitatively by diastereomeric salt formation with (–)-quinine. The (+)-isomer was retrieved from the less-soluble quininium salt. Racemate crystals, (plusmn;)-1, are monoclinic, space group P2₁/c, a = 7.609(4)Å, b = 16.731(7)Å, c = 10.746(5) Å, = 99.83(4)° enantiomeric crystals, (+)-1, are monoclinic, space group P2₁, a = 5.857(2)Å, b = 15.282(4)Å, c = 7.618(2)Å, = 95.62(2)°. Molecular packing is similar in the two structures; the enantiomer has a 0.7% higher volume per molecule and the lower fusion temperatures by 3°C. In both structures, carboxylic acids donate hydrogen bonds to the amide carbonyls of adjacent molecules without reciprocation. Amides form three-centered hydrogen bonds to carboxy oxygen of an intramolecular carboxylic acid group and to oxygen of a ketone carbonyl in an adjacent molecule.     

Monte Carlo free energy calculations using electronic structure methods

The molecular mechanics-based importance sampling function (MMBIF) algorithm [R. Iftimie, D. Salahub, D. Wei, and J. Schofield, J. Chem. Phys. 113, 4852 (2000)] is extended to incorporate semiempirical electronic structure methods in the secondary Markov chain, creating a fully quantum mechanical Monte Carlo sampling method for simulations of reactive chemical systems which, unlike the MMBIF algorithm, does not require the generation of a system-specific force field. The algorithm is applied to calculating the potential of mean force for the isomerization reaction of HCN using thermodynamic integration. Constraints are implemented in the sampling using a modification of the SHAKE algorithm, including that of a fixed, arbitrary reaction coordinate. Simulation results show that sampling efficiency with the semiempirical secondary potential is often comparable in quality to force fields constructed using the methods suggested in the original MMBIF work. The semiempirical based importance sampling method presented here is a useful alternative to MMBIF sampling as it can be applied to systems for which no suitable MM force field can be constructed.     

A note on the numerical solution of a periodic parabolic problem

A direct method is presented for the numerical determination of solutions of the heat conduction equation having periodT in time. A simple error analysis which improves previous results is given.     

C. fumago chloroperoxidase is also a dehaloperoxidase: oxidative dehalogenation of halophenols

We have examined the H2O2-dependent oxidative dehalogenation of 2,4,6-trihalophenols and p-halophenols catalyzed by Caldariomyces fumago chloroperoxidase (CCPO). CCPO is significantly more robust than other peroxidases and can function under harsher reaction conditions, and so its ability to dehalogenate halophenols could lead to its use as a bioremediation catalyst for aromatic dehalogenation reactions. Optimal catalysis occurred under acidic conditions (100 mM potassium phosphate solution, pH 3.0). UV-visible absorption spectroscopy, high-performance liquid chromatography, and gas chromatography/mass spectrometry clearly identified the oxidized reaction product for CCPO-catalyzed dehalogenation of 2,4,6-trihalophenols as the corresponding 2,6-dihalo-1,4-benzoquinones. This reaction has previously been reported for two His-ligated heme-containing peroxidases (see Osborne, R. L.; Taylor, L. O.; Han, K. P.; Ely, B.; Dawson, J. H. Biochem. Biophys. Res. Commun. 2004, 324, 1194-1198), but this is the first example of a Cys-ligated heme-containing peroxidase functioning as a dehaloperoxidase. The relative catalytic efficiency (turnover number) of CCPO reported herein is comparable to that of horseradish peroxidase (Ferrari, R. P.; Laurenti, E.; Trotta, F. J. Biol. Inorg. Chem. 1965, 4, 232-237). The mechanism of dehalogenation has been probed using p-halophenols as substrates. Here the major product is a dimer with 1,4-benzoquinone as the minor product. An electron-transfer mechanism is proposed that accounts for the products formed from both the 2,4,6-trihalo- and p-halophenols. Finally, we note that this is the first case of a peroxidase known primarily for its halogenation ability being shown to also dehalogenate substrates.     

WADM and radiation MHD simulations of compact multi-planar and cylindrical wire arrays at 1 MA currents

The radiative performance of Z-pinches created by the imploding wire array loads is defined by the ablation and implosion dynamics of these loads. Both these processes can be effectively modeled by the Wire Ablation Dynamics Model (WADM), which extends the formalism exploited earlier for the cylindrical wire arrays to the loads of arbitrary geometries. The WADM calculates the ablation rates for each array wire and provides the important dynamic parameters, such as the specific mass and velocity of the imploding plasma, which can be used to estimate the shapes of the x-ray pre-pulse and, partially, the main x-ray burst. The applications of the WADM also extend to combined material wire array loads. The ablation and implosion dynamics of novel Prism Planar Wire Array (PPWA) and combined material (Mo/Al/Mo) Triple Planar Wire Array (TPWA) loads are discussed in detail. The combined WADM and radiation MHD simulation is applied to model the radiative performance of the precursor plasma column, created by the imploding stainless steel compact cylindrical wire array. As the radiation effects intensify with the mass accumulation at the array center, the simulation reveals the transformation of quasi-uniform precursor column into a heterogeneous plasma structure with strong density and temperature gradients. We find that radiative performance of the precursor plasma is greatly affected by the load geometry as well as by the wire material.     

Transition metal derivatives of 1,1′-dichloroferrocene

Complexes of the general formula [Cl₂Fc] _nML, (Cl₂Fc = C1C₅H₄FeC₅H₃Cl; ML = Fe(CO)₂C₅H₅, AuP(C₆H₅)₃, Mn(CO)₅ or Ir(CO)[P(C₆H₅)₃]₂ when n = 1; ML = Ti(C₅H₅)₂ when n = 2) have been prepared from a salt elimination reaction between 1,1′-dichloro-2-lithioferrocene and transition metal halide complexes. Spectroscopic properties of the compounds are reported. The titanium complex exists in meso and dl forms.     

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