Poly(3-hydroxybutyrate)-depolymerase from Pseudomonas lemoignei: catalysis of esterifications in organic media

Lipase catalysis in nonaqueous media is recognized as a powerful tool in organic and more recently polymer synthesis. Even though none of the currently known polyhydroxyalkanoate (PHA) depolymerases have lipase activity, they do have a catalytic center that resembles that of lipases. Motivated by the above, the potential of using the poly(3-hydroxybutyrate), PHB, depolymerase from Psuedomonas lemoignei in organic media to catalyze ester-forming reactions was investigated. The effect of different organic solvents (benzene-d(6), cyclohexane-d(12), and acetonitrile-d(3)) on the activity of the PHB-depolymerase toward propylation of L-lactide was studied. A significant difference in the catalytic rate was observed as a function of solvent polarity. The selectivity of the PHB-depolymerase (P. lemoignei) to catalyze the propylation of a series of different lactones including epsilon-caprolactone, delta-butyrolactone, gamma-butyrolactone, and D, L, meso, and racemic lactides has been studied with the PHB-depolymerase (P. lemoignei) in organic solvents. Important differences in the reactivity of these lactones, as well as selective hydrolysis of stereochemically different linear lactic acid dimers, were observed. Moreover, the ability of the PHB-depolymerase to catalyze the solventless polymerization of epsilon-caprolactone and trimethylene carbonate was investigated.     

Capillary electrophoretic determination of zinc dimethyldithiocarbamate (Ziram) and zinc ethylenebisdithiocarbamate (Zineb)

A simple and sensitive capillary electrophoretic method was developed for the separation and determination of Ziram and Zineb in boric acid buffer by direct UV absorbance detection at lambda=254 nm. The separation is dependent on pH and nature of the buffer. The detection limits (S/N=3) are 1.88x10(-6) mol/l (0.57 mug/ml) and 2.48x10(-6) mol/l (0.68 mug/ml) for Ziram and Zineb, respectively. The method was successfully applied to the analysis of wheat samples spiked with Ziram and Zineb.     

Linear phase FIR approximation of magnitude response |1/ω| for maximal flatness at an arbitrary frequency ω0, 0<ω0<π*

In many signal processing situations, the desired (ideal) magnitude response of the filter is a rational function: (a digital integrator). The requirements of a linear phase response and guaranteed stable performance limit the design to a finite impulse response (FIR) structure. In many applications we require the FIR filter to yield a highly accurate magnitude response for a narrow band of frequencies with maximal flatness at an arbitrary frequency ₀ in the spectrum (0, ). No techniques for meeting such requirements with respect to approximation of are known in the literature. This paper suggests a design by which the linear phase magnitude response can be approximated by an FIR configuration giving a maximally flat (in the Butterworth sense) response at an arbitrary frequency ₀, 0<₀<^*. A technique to compute exact weights for the design has also been given.     

Synthesis,characterization and reactivity of electrophilic mono- and binuclear nitrosyls of osmium(II)ketoximates

The reaction of [OsX₂(HL)(L)] (1) {X = Cl or Br; HL = PhC(O)C(=NOH)Ph (HL¹) or PhC(O)C(=NOH)Me (HL2)] with n-BuONO yields mononuclear [OsX(NO)(L¹)₂] (2) or binuclear [OsX₂(NO)(L²)]₂2 (3) nitrosyls depending on L. The complexes are also obtained by reacting (1) with NaNO₂ plus HCl. Molecular weight determinations are in agreement with mono- and binuclear formulations. The diamagnetic orange-red nitrosyls exhibit (NO) at ca. 1890 cm^–1 indicating NO⁺ character of the bound nitrogen monoxide. In ¹H-n.m.r. a single sharp L² methyl signal is in line with the centrosymmetric geometry (4) of the binuclear nitrosyls. The complexes display both spin-allowed and -forbidden charge transfer transitions in the 1000–200 nm range. Both (2) and (3) are electroactive and reductions characteristic of mono- and binuclear compositions are observable on the negative side of s.c.e. They react smoothly with acetylacetone (acacH) in the presence of K2CO3 yielding K[Os(acamo)(L1)2] (5) and K[Os(acac)(acamo)(L2)] (6) [acamo = deprotonated MeC(O)C(=NOH)C(O)Me] respectively.     

Effect of the alpha-methyl substituent on chemoselectivity in esterase-catalyzed hydrolysis of S-acetyl sulfanylalkanoates

The isomeric compounds 1 and 3, which differ only in the position of a methyl substituent, give opposite chemoselectivities in an esterase-catalyzed hydrolysis reaction. The esterase was chemoselective for the oxoester in 1, but for the thiol ester group in 3. A high enantioselectivity was observed for both 1 and 3.     

Multiple scattering of gamma rays in water,concrete and sand

The transmitted photon spectra of¹³³Ba,²²Na,¹³⁷Cs,⁵⁴Mn and⁶⁰Co point sources are measured through different thicknesses of water, concrete and sand. The multiple-scatter peaks observed in these materials at 60, 90 and 100 keV energies respectively are found to be independent of incident photon energy and thickness of the medium.     

Investigation of phonon anomalies in intermediate valence compounds SmS and Sm0·65Y0·25S

Phonon anomalies in two intermediate valence compounds (IVC), SmS and Sm_0·75Y_0·25S have been investigated using breathing shell model (BSM). The BSM includes breathing motion of electron shells of the rare earth atom due tof−d hybridization. The phonon dispersion curves of IVC, calculated from the present model, agree well with the measured data. One-phonon density of states calculated from the present model compares well with the Raman spectra.     

Estimation of a random coefficient model under linear stochastic constraints

Summary A random coefficient model in which means of random coefficients are subject to a set of linear stochastic constraints is considered and estimators for the means of coefficients are proposed. Their asymptotic properties are presented and some remarks on efficiency are placed.