A new and sensitive method for the spectrophotometric determination of ethion in environmental and biological samples

A new and sensitive spectrophotometric method is described for the determination of sub ppm levels of the organophosphorus pesticide ethion based on the oxidation of ethion by potassium permanganate in phosphoric acid to sulphones and its hydrolysis under acidic condition at 100°C to release formaldehyde, which is then determined by a reaction with 1,3,5-trihydroxybenzene (phloroglucinol) in alkaline medium. Beer's law is obeyed in the range of 0.1–0.8 ppm of ethion at 460 nm. The analytical parameters have been optimized.     

Comparative energetics of glucose and xylose metabolism in ethanologenic recombinantEscherichia coli B

This study compared the anaerobic catabolism of glucose and xylose by a patented, recombinant ethanologenicEscherichia coli B 11303:pLOI297 in terms of overall yields of cell mass (growth), energy (ATP), and end product (ethanol). Batch cultivations were conducted with pH-controlled stirred-tank bioreactors using both a nutritionally rich, complex medium (Luria broth) and a defined salts minimal medium and growth-limiting concentrations of glucose or xylose. The value of Y_ATP was determined to be 9.28 and 8.19 g dry wt cells/mol ATP in complex and minimal media, respectively. Assuming that the nongrowth-associated energy demand is similar for glucose and xylose, the mass-based growth yield (Y _x/s , g dry wt cells/g sugar) should be proportional to the net energy yield from sugar metabolism. The value ofY _x/s was reduced, on average, by about 50% (from 0.096 g/g glu to 0.051 g/g xyl) when xylose replaced glucose as the growth-limiting carbon and energy source. It was concluded that this observation is consistent with the theoretical difference in net energy (ATP) yield associated with anaerobic catabolism of glucose and xylose when differences in the mechanisms of energy-coupled transport of each sugar are taken into account. In a defined salts medium, the net ATP yield was determined to be 2.0 and 0.92 for glucose and xylose, respectively.     

Compounds of nickel(II) with 5SR,7RS,12SR,14SR-5,12-dimethyl-7,14-diphenyl-1,4,8,11-tetraazacyclotetradecane, rmL: The structures of [Ni(rmL)](ClO4)2 · 0.5H2O and cis-[Ni(rmL)(acac)]ClO4

The imine functions of [Ni(mL¹)](ClO₄)₂ (mL¹ = meso-7RS,14SR-5,12-dimethyl-7,14-diphenyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene) are reduced by using NaBH₄ in acetonitrile/methanol to form the meso–meso and rac–meso isomeric cyclic tetramine complex cations [Ni(mmL²)]²⁺ and [Ni(rmL²)]²⁺ (mml² = 5RS,7RS,12SR,14SR- and rmL² = 5SR,7RS,12SR,14SR-5,12-dimethyl-7,14-diphenyl-1,4,8,11-tetraazacyclotetradecane) in ca. 8:1 proportions. [Ni(rmL²)]²⁺ is also prepared from rmL², formed in <1% yield by the reduction of mL¹ by NaBH₄ in ethanol. Square planar singlet ground state (S = 1) salts [Ni(rmL²)](ClO₄)₂ and [Ni(rmL²)][ZnCl₄] and triplet ground state (S = 3) trans-di-ligand octahedral compounds trans-[Ni(rmL²)X₂] ,μ-Y-trans-[Ni(rmL²)Y] and folded macrocycle compounds cis-[Ni(rmL²)(acac)]CIO₄ (acac⁻ = pentane-2,4-dionato), cis-[{Ni(rmL²)}₂(C₂O₄)](ClO₄)₂, cis-[Ni(rmL²)(H₂O)₂](ClO₄)₂ and cis-[Ni(rmL²)X₂], X⁻ = Cl⁻, Br⁻, are described. The S = 1 salt 1SR,4SR,5SR,7RS,8RS,11RS,12SR,14SR-[Ni(rmL²)](ClO₄)₂ · 0.5H₂O has a disordered structure with Ni(II) in square planar coordination by the nitrogen atoms of the macrocycle, in N-configuration III, with Ni–N_mean = 1.96(2) Å. The six-membered chelate rings both have chair conformations, with the phenyl substituents equatorially oriented and with the methyl substituents disordered over axial and equatorial orientations. The S = 3 compound cis-1SR,4SR,5SR,7RS,8SR,11SR,12SR,14SR-[Ni(rmL²)(acac)]ClO₄ has N-configuration V. The macrocycle is folded along N¹–Ni–N⁸, adjacent to the phenyl substituents {N1–Ni–N8 = 176.45(6), N4–Ni–N11 = 98.16(6)°}, with mean Ni–N = 2.09(2) Å and mean Ni–O = 2.121(5) Å. Both six-membered chelate rings have chair conformations with the methyl substituents equatorially oriented, while one has the phenyl substituent equatorially and the other has it axially oriented. The structures of the isomeric [M(rmL²)(acac)]ClO₄, [M(rrL²)(acac)]CIO₄ and [M(mmL²)(acac)]ClO₄ compounds are compared.     

Determination of total taurine in pet foods by liquid chromatography of the dansyl derivative: collaborative study

A liquid chromatographic (LC) method for the determination of total taurine in pet foods was evaluated in a collaborative study. Ten laboratories assayed 6 blind duplicate pairs of wet and dry pet foods. The taurine in the 6 sample pairs ranged from low (170 mg/kg) to high (2250 mg/kg) concentrations as is. Collaborators also assayed a sample of known taurine concentration for familiarization purposes. Samples were hydrolyzed to release bound taurine, which was subsequently converted to the dansyl derivative and quantitated by gradient-elution LC with fluorescence detection. Repeatability relative standard deviations, RSDr, ranged from 3.2 to 10.0%; reproducibility relative standard deviations, RSDR, ranged from 6.1 to 16.1%. The method has been adopted Official First Action status by AOAC INTERNATIONAL.     

ISO radiation sterilization standards

This presentation provides an overview of the current status of the ISO radiation sterilization standards. The ISO standards are voluntary standards which detail both the validation and routine control of the sterilization process. ISO 11137 was approved in 1994 and published in 1995. When reviewing the standard you will note that less than 20% of the standard is devoted to requirements and the remainder is guidance on how to comply with the requirements.

Future standards developments in radiation sterilization are being focused on providing additional guidance. The guidance that is currently provided in informative annexes of ISO 11137 includes: device/packaging materials, dose setting methods, and dosimeters and dose measurement, currently, there are four Technical Reports being developed to provide additional guidance:

1. 1. AAMI Draft TIR, “Radiation Sterilization Material Qualification”

2. 2. ISO TR 13409-1996, “Sterilization of health care products — Radiation sterilization — Substantiation of 25 kGy as a sterilization dose for small or infrequent production batches”

3. 3. ISO Draft TR, “Sterilization of health care products — Radiation sterilization Selection of a sterilization dose for a single production batch” li]4. ISO Draft TR, “Sterilization of health care products — Radiation sterilization-Product Families, Plans for Sampling and Frequency of Dose Audits.”

     

Thermochemical investigations of hydrogen-bonded solutions. Part 11. Expressions for predicting anthracene solubilities in alcohol+alkoxyalcohol mixtures based on mobile order theory

Experimental solubilities are reported for anthracene dissolved in eight binary mixtures containing 2-ethoxyethanol with 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-pentanol, 3-methyl-1-butanol and 1-octanol, and also in binary 1-pentanol+2-methoxyethanol and 2-methyl-1-propanol+2-propoxyethanol solvent systems at 25°C. Results of these measurements, combined with previously reported anthracene solubility data in 22 different alcohol +2-alkoxyethanol (2-methoxyethanol, 2-propoxyethanol and 2-butoxyethanol) solvent mixtures, are used to test the limitations and applications of expressions derived from Mobile Order theory. The first predictive expression assumes only formation of homogeneous self-associated hydrogen-bonded species, whereas the second equation includes additional terms to account for heterogeneous complex formation between the dissolved alcohol and 2-alkoxyethanol solvent molecules. Both equations predict the observed anthracene solubilities to within an average absolute deviation of about 3%.     

Ab initio calculations of the ground-state potential energy surface for the C?F bond decomposition in n-fluoropropane within the method for approximation of the frozen molecular fragment

The recently proposed ab initio method for calculation on many-electron molecular systems with the approximation of the inactive part of a molecule by a frozen molecular fragment was tested further in a case of the dissociation reaction of the C? F bond in n-fluoropropane. Results from the Hartree–Fock, multiple reference double-excitation configuration–interaction and second-order Møller–Plesset methods are presented. The reproduction of potential energy surfaces as well as the reproduction of electron density distribution are in excellent agreement with extended basis-set calculations. Different choices of fragments to be frozen have been examined.     

“Model-free” kinetic analysis?

All kinetic analyses aim to determine a sufficient number of kinetic parameters, usually at least an apparent Arrhenius activation energy and pre-exponential factor, and a conversion function or kinetic model (making up a ‘kinetic triplet’), so that accurate extrapolations of kinetic behaviour can be made. “Model-free” methods of kinetic analysis postpone the problem of identifying a suitable kinetic model until an estimate of the activation energy has been made. A major reason for doing this is that misidentification of the kinetic model has a marked effect on the values obtained for the Arrhenius parameters in both isothermal and non-isothermal kinetic analyses. Some aspects of this problem are discussed.

The non-parametric kinetics (NPK) method [1 and 2] is a “model-free” method of kinetic analysis that does not seem to have received the attention that it deserves. This is probably because of its mathematical sophistication and the fact that the matrix and non-linear regression calculations involved are not readily automated. The principle of the method appears to be that of “forcing” a set of non-isothermal data into the set which should have been obtained if the experiments had been carried out isothermally. The method deserves wider testing and also raises some interesting aspects of the philosophy behind non-isothermal kinetic analysis.     

Ab initio MRD–CI calculations on cubane (neutral,carbocation, carboanion) and dissociation of nitrocubanes based on localized orbitals

Ab initio MRD –CI calculations based on localized orbitals were carried out for cubane (neutral, carbocation, carboanion) both in our customary MODPOT basis set and in an all-electron 4–31G basis set. The calculated MRD –CI charge distributions on C1 (the skeletal atom from which the H^? or H⁺ was removed) (ab initio MODPOT neutral 4.221, carbocation 3.796, carboanion 4.282; all-electron 4–31G neutral 6.171, carbocation 5.717, carboanion 6.078) indicate that the + or - charge does not remain localized on C1 but redistributes itself. This has significant implications for preparative reactions of energetically substituted cubanes. The MRD –CI population analyses differ somewhat from the SCF population analyses, especially in the calculated total overlap populations. To investigate this effect on electrostatic molecular potential contour (EMPC ) maps generated from SCF or MRD –CI wave functions, we wrote additional routines to calculate EMPC maps from MRD –CI wave functions. The EMPC maps generated from SCF or MRD –CI wave functions are different if the molecule needs an MRD –CI multideterminant wave function to describe it adequately. The EMPC map is a one-electron property. One-electron properties are derived from the 1-matrix. The 1-matrix is different for SCF or MRD –CI wave functions. Thus, all the one-electron properties (EMPC maps, population analyses, bond deviation indices, etc.) are different when calculated from SCF or MRD –CI wave functions if MRD –CI wave functions are necessary to describe a system properly. We calculate these one-electron properties from the 1-matrix from the final natural orbitals. Our preliminary calculations for the dissociation pathway indicate it takes more energy to dissociate a bond in 1-nitrocubane than in octanitrocubane. Even in their ground electronic states at equilibrium geometry, both 1-nitrocubane and octanitrocubane require MRD –CI wave functions to describe them properly. The c² of the single determinant SCF wave function is only 0.8401 for 1-nitrocubane and 0.8300 for octanitrocubane. There are contributions from skeletal excitations as there are for cubane itself as well as excitations involving the nitrogroup. As the bond in nitrocubane is dissociated to 8.00 bohrs, the c² of the SCF contribution drops to only 0.4606 (1-nitrocubane) and 0.4445 (octanitrocubane). At this C₁? N₁ intermolecular distance, the largest excitations are in the C₁? N₁ bond: (C₁? N₁)² → (C₁? N₁*)², (C₁? N₁) → (C₁? N₁*). We also calculated the first electronically excited state for the dissociation pathway for selected points for both 1-nitrocubane and octanitrocubane.