Butyrate production from carbon monoxide byButyribacterium methylotrophicum

Applied Biochemistry and Biotechnology - Carbon monoxide is produced in high concentrations by gasification of coal or biomass, and is a potentially inexpensive feedstock for biological processes....     

Density dependence of electron mobility in dense gases

The density (N) dependence of electron mobility (μ) in various dense gases (H₂, N₂, O₂, CO₂ and rare gases) has been calculated using a multiple-scattering approach. Deviation of the high density gas from its perfect gas behaviour has been taken into account through the temperature-dependent second virial coefficient. Multiple scattering of electrons leads to shifts in their kinetic energy and it also changes their distribution functions. This unified approach predicts both positive and negative effects. The positive (negative) effect entails on increase (decrease) of μ withN. We have assessed the available data on momentum transfer cross-sections by comparing the mobility at very low densities (Nμ)₀ with experimental results. The density dependence is studied by comparing the calculated ratioNμ)/Nμ)₀ with the observed values and other theoretical work. The Legler model which assumes a constant cross-section is inadequate for predicting the observed density dependence. We obtain good agreement with available experimental work for all the atomic and molecular species studied here.     

A sensitive solid-phase fluoroimmunoassay for detection of opiates in urine

An automated flow fluorometer designed for kinetic binding analysis was adapted to develop a solid-phase competitive fluoroimmunoassay for urinalysis of opiates. The solid phase consisted of polymer beads coated with commercial monoclonal antibodies (MAbs) raised against morphine. Fluorescein-conjugated morphine (FL-MOR) was used as the fluorescein-labeled hapten. The dissociation equilibrium constant (K _D ) for the binding of FL-MOR to the anti-MOR MAb was 0.23 nM. The binding of FL-MOR to the anti-MOR MAb reached steady state within minutes and was displaced effectively by morphine and other opiates. Morphine-3-glucuronide (M3G), the major urinary metabolite of heroin and morphine, competed effectively with FL-MOR in a concentration-dependent manner for binding to the antimorphine MAb and was therefore used to construct the calibration curve. The sensitivity of the assay was 0.2 ng/mL for M3G. The assay was effective at concentrations of M3G from 0.2 to 50 ng/mL, with an IC₅₀ of 2 ng/mL. Other opiates and heroin metabolites that showed >50% crossreactivity when present at 1 μg/mL included codeine, morphine-6-glucuronide, and oxycodone. Methadone showed very low crossreactivity (<5%), which is a benefit for testing in patients being treated for opiate addictions. The high sensitivity of the assay and the relatively high cutoff value for positive opiate tests allows very small sample volumes (e.g., in saliva or sweat) to be analyzed. A double-blind comparison using 205 clinical urine samples showed good agreement between this single-step competitive assay and a commercially performed enzyme multiplied immunoassay technique for the detection of opiates and benzoylecgonine (a metabolite of cocaine).     

After-effects of Auger ionization following electron capture in organic 125iodine compounds

The emission Mössbauer spectra of ¹²⁵I labeled iodobenzene, methyl iodide, and of their dilute solutions in benzene and hexane, were computer analyzed. Two species were observed, in one of which tellurium is presumably attached to two organic moieties, while in the other, tellurium is attached to a single organic moiety.     

Interfacial phase transition of an environmentally responsive elastin biopolymer adsorbed on functionalized gold nanoparticles studied by colloidal surface plasmon resonance

The change in optical properties of colloidal gold upon aggregation has been used to develop an experimentally convenient colorimetric method to study the interfacial phase transition of an elastin-like polypeptide (ELP), a thermally responsive biopolymer. Gold nanoparticles, functionalized with a self-assembled monolayer (SAM) of mercaptoundecanoic acid onto which an ELP was adsorbed, exhibit a characteristic red color due to the surface plasmon resonance (SPR) of individual colloids. Raising the solution temperature from 10 degrees C to 40 degrees C thermally triggered the hydrophilic-to-hydrophobic phase transition of the adsorbed ELP resulting in formation of large aggregates due to interparticle hydrophobic interaction. Formation of large aggregates caused a change in color of the colloidal suspension from red to violet due to coupling of surface plasmons in aggregated colloids. The surface phase transition of the ELP was reversible, as seen from the reversible change in color upon cooling the suspension to 10 degrees C. The formation of colloidal aggregates due to the interfacial phase transition of adsorbed ELP was independently verified by dynamic light scattering of ELP-modified gold colloids as a function of temperature. Colloidal SPR provides a simple and convenient colorimetric method to study the influence of the solution environment, interfacial properties, and grafting method on the transition properties of ELPs and other environmentally responsive polymers at the solid-water interface.     

Transport of excitation energy in a doped molecular aggregate. III. numerical investigation of exciton hopping with various exciton-depleting processes

A brute-force numerical investigation has been carried out on the hopping of excitons in a three-dimensional molecular aggregate. Possibilities of vibronic decay, rapid chemical reactions of saturated species, radiative decay of overpopulated molecules, and cooperative chemical reactions involving saturated exciton populations on traps of two different types have been considered. Investigation have been performed with two types of initial distribution of excitons—facial and random—and for 10,000 or, sometimes, for 20,000 time steps each of duration 1ps. Several interesting observations have been made from this computer experiment: (1) The total number of occurrences of fast reactions depends upon the initial distribution of excitons. (2) It decreases if other exciton depleting processes are at work. (3) It also depends on the pattern of placement of traps. (4) The location of impurities also affects the rate of occurrence of these reactions. Thus, more reactions occur when the excitons are initially concentrated on one face and traps are suitably located on the path of flow of these excitons. A random initial distribution tends to equilibrate the excitons quickly over all the lattice points, thus giving rise to fewer reactions. (5) The number of reactions need not necessarily increase with the number of reaction centers; in fact, it decreases as more centers are added when the supply of excitons is severely limited. (6) A Complicated dynamics results when different types of additional processes, viz., enhanced fluorescence, radiative emissions, and cooperative chemical reactions are simultaneously allowed. The cooperative process has been clearly found to dominate. A first-order rate constant of about 10⁸ s-¹ has been calculated for the occurrence of the cooperative process. This rate is affected when other nonconserving processes are switched on. Observations (1), (4), and (5) are the most important conclusions of our work. They lie outside the scope of traditional models such as the random walk model, the diffusion model, and the lattice model for the migration of excitons in a molecular aggregate. © 1993 John Wiley & Sons, Inc.     

Diaminodithioether complexes of nickel(II) and palladium(II): A unique case of dealkylation of S,S′-thioether

Summary Nickel(II) and palladium(II) complexes of the 1,3-di(o-aminophenylthio) propane (H₂L¹) and 1,2-di(o-aminophenylthio)xylene (H₂L²) ligands have been prepared and characterized. The hydrobromide salt of H₂L¹ gave a 12 ligand-metal complex of Pd^II, whereas free H₂L¹ formed the usual 1:1 species. The reaction of Na₂PdCl₄ with H₂L² resulted in S,S-dealkylation of the ligand and formation of a mononuclear complex of the corresponding thiol, i.e. 2-aminobenzenethiol. NiCl₂, NiBr₂ and Ni(ClO₄)₂ did not react directly with H₂L². Ni^II is a fairly hard ion and therefore does not coordinate to the soft thioether moiety in H₂L² in the absence of soft anions which symbiotically motivate Ni^II to act as a soft acceptor. It thus does not react with H₂L² in the presence of hard ions such as Cl^–, Br^- and ClO ₄ ^– , but, the in situ reaction of the constituents produced the tetrahedral Ni^II complex, contrary to earlier reports of similar types of octahedral species.     

Transformed Dirac equation for the hydrogen atom,comparison with previous approaches in momentum space,and the anomalous Zeeman effect in momentum representation

The solution of a unitarily transformed Dirac equation for the hydrogenic electron in zero magnetic field is investigated here. The momentum‐space representation is adopted as a natural recourse. The spinor part of the transformed wavefunction in momentum space can be easily prescribed for a central potential. Hence, for the Coulomb potential, a pair of equations is obtained for the radial components in momentum space. It is shown that starting from these radial equations, one can recover the equations previously derived by Rubinowicz, Lévy, and Lombardi for the problem of the Dirac hydrogen atom in momentum space. This establishes equivalence among different approaches based on the momentum representation, including the current treatment. The recovery of the equations due to Rubinowicz permits the exact eigenvalues to be written down and exact expressions to be derived for the radial components of the transformed wavefunction in momentum space. A new approach is adopted to carry out a reduction to the nonrelativistic regime and the nonrelativistic limit. At first the transformed momentum‐space equation for the hydrogen atom is rewritten in terms of the hyperspherical coordinates. The zeroth‐order solutions of the new equation are recovered in the limit c → ∞ where c is the speed of light. These are manifestly separable into positive‐ and negative‐energy forms. For positive energy, these solutions have nonvanishing upper components that are two‐component spinors. The latter exactly correspond to the single‐component, nonrelativistic, momentum‐space solutions derived by Fock. It is shown that when the upper component is corrected through first order in v²/c² but the separability is still maintained for the transformed wavefunction, one retrieves the Pauli equation in momentum space. It is also shown that for a hydrogen atom placed in a uniform magnetic field, the nonvanishing momentum‐space matrix elements representing the anomalous Zeeman effect have a simple form, namely, the product of a radial integral and an angular integral. These integrals are equal to the well‐known radial and angular integrals in coordinate representation. The matrix elements can be easily evaluated. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003     

Studies on metal — protein interactions: Inter-comparison among various approaches

Binding ability of mercury, thallium, lead and bismuth with Erythrina variegata seed protein have been investigated using tracer packet technique. Due to the lack of standard methods, inter-comparisons have been made among three different approaches, like trichloroacetic acid (TCA) precipitation, isoelectric precipitation and dialysis of protein after incubation with the metals. Good agreement was observed for all the cases except that of lead.