MCSCF reaction-path energetics and thermal rate-constants for the reaction of3NH with H2

Summary The intrinsic reaction-path, reactants, transition state and products for the reaction of NH (^3–)+H₂ (¹ _g ⁺ ) NH₂ (²B₁)+H (²S) involving the lowest triplet electronic state of NH₃ were calculated using multi-configuration (MC) SCF methods. The calculated change of internal energy for the reaction of 11.0 kcal mol^–1 agrees with the experimental value within 2 kcal mol^–1. The barrier to reaction is 23.4 kcal mol^–1 high. The harmonic MCSCF reaction-path potential was calculated and canonical variational transition state theory calculations of the rate constants performed over a temperature range from 400 to 2500 K. The computed rate constants are generally two orders of magnitude smaller than those of the comparable reaction of OH with H₂, whereas those of the reverse reaction are by a factor of 20 larger than those of OH₂ with H.     

Direct detection of oxygen intermediates in the non-heme Fe enzyme taurine/alpha-ketoglutarate dioxygenase

The reaction of substrate-bound taurine/alpha-ketoglutarate dioxygenase with O2 has been studied using cryogenic continuous-flow spectroscopy. Transient absorption spectra acquired at -38 degrees C show an exponential decay of a 318-nm chromophore with an apparent rate of 1.3 s-1. The observed optical changes and their kinetics are consistent with the profile of an Fe(IV) species detected recently by M?ssbauer spectroscopy (Price et al., Biochemistry 2003, 42, 7497-7508). Resonance Raman measurement upon excitation at 363.7 nm reveal at least two oxygen isotope-sensitive vibrations at 821/787 cm-1 and 583/555 cm-1 for 16O and 18O derivatives, respectively. An additional mode is likely to be obscured by an ethylene glycol vibration at 865 cm-1 and/or 1089 cm-1. The 821 cm-1 vibration is assigned to the stretching mode of Fe(IV)=O species on the basis of its frequency and isotopic shift amplitude. The 583 cm-1 band is likely to originate from an Fe-O2 precursor of the Fe(IV)=O species, although its structural details are unclear at present.     

Effects of electric fields and electric field-gradients on X-ray scattering factors and the compton profile of hydrogenic atoms

Analytic expressions for the modification of the hydrogenic atom X-ray atomic scattering factor and Compton profile due to a proton at distance R are derived. It is shown that electric field-gradient effects (order R^?3) are comparable in importance to electric field effects (order R^?2).     

The spatial distribution of poly(methyloctylsiloxane) deposited by solvent evaporation in the pores of HPLC silica particles

Summary Poly(methyloctylsiloxane) (PMOS), sorbed into the pores of HPLC silica particles by solvent evaporation, can function as a useful stationary phase for reversed-phase chromatography. The present work addresses the question of how the PMOS is distributed in the pores. Measurements of the surface area (BET, N₂) of a series of partially loaded samples (0–40% PMOS, m/m) using a typical batch of HPLC silica (10 μm irregular particles with 6 nm pores) show that the specific surface area of the samples decreases linearly with the specific loading (mass of PMOS per gram of silica). This result is not consistent with a “film” model in which the PMOS is deposited uniformly on the pore walls, but is consistent with a model in which long segmented “plugs” of PMOS are deposited within the pore system. Presented at the 21^st ISC held in Stuttgart, Germany, 15^th–20^th September, 1996     

Sulphate preconcentration by anion exchange resin in flow injection and its turbidimetric determination in water

A preconcentration procedure was established for sulphate determination in rain waters at the mg/l level, employing a small column packed with the AG1-X8 (200-400 mesh) anionic resin inserted into a flow injection system. Sulphate determination was performed by using the turbidimetric method based on reaction with barium. For concentrations within 0.10 and 2.0 MgSO(2-)(4)/l, a throughput of 50 determinations/hr was achieved, and the relative standard deviation of results was better than 2%.     

Investigating bidentate and tridentate carbamoylmethylphosphine oxide ligand interactions with rare-Earth elements using electrospray ionization quadrupole ion trap mass spectrometry

Electrospray ionization (ESI) quadrupole ion trap mass spectrometry (QIT-MS) and collisionally activated dissociation (CAD) were used to evaluate the rare-earth binding properties of two hydrophobic carbamoylmethylphosphine oxide (CMPO) ligands, the normal bidentate variety, (t-BuC6H4)2P(O)CH2C(O)N(i-Bu)2 (A), a new potentially tridentate extractant, (t-BuC6H4)2P(O)CH[CH2C(O)N(i-Bu)2]C(O)N(i-Bu)2 (B), and tributyl phosphate. The mass spectral results obtained from analysis of 1% HNO3/methanol solution containing the ligands and dissolved lanthanide salts reveal that the favorable stoichiometries of the ligand/metal/nitrate complexes are 2:1:2 for the bidentate ligand A, 1:1:2 for the tridentate ligand B, and 3:1:2 for the monodentate tributyl phosphate. These observed stoichiometries correlate with the number of available binding sites on each ligand as well as with potential steric effects. Energy-variable collisionally activated dissociation experiments showed that for the 2:1:2 complexes involving ligand A or B, as the ionic radius of the bound metal decreased, the removal of nitric acid required less energy and resulted in less extensive spontaneous solvent coordination. This experimental trend suggests that, as the ionic radius of the lanthanide ion decreases, a pair of the carbamoylmethylphosphine ligands is able to more completely solvate the bound metal ion thereby weakening the nitrate-metal interaction.     

Label-free chiral detection of melittin binding to a membrane

The study presented here describes an innovative approach for the detection of surface-confined proteins using chiral second harmonic generation (C-SHG). A unique optical geometry has been employed which allows for the separation of the chiral and achiral nonlinear response. By utilizing this optical arrangement, the detection of chirality originating from melittin adsorbed to a planar supported lipid bilayer has been performed for the first time by C-SHG. Melittin binding to the membrane was monitored as a function of bulk concentration through detection of the C-SHG signal. Analysis of the C-SHG adsorption isotherms reveals Frumkin adsorption behavior with a positive interaction energy. The binding constant (Ka) obtained was determined to be (8.3 +/- 1.0) x 105 M-1. The results of these studies have far-reaching implication in the use of C-SHG for the label-free detection of protein association to surfaces and in the analysis of protein interfacial phenomena.     

Carbon dioxide emulsion assisted loading of polymer microspheres toward sustained release materials

An organic solvent-free method for encapsulating progesterone at high loadings within micron-sized inert latex polymer beads is reported. This approach makes use of a polymeric surfactant to emulsify carbon dioxide into an aqueous latex suspension. In this way, preformed approximately 4 microm polystyrene (PS) microparticles surface-grafted with poly(N-vinylpyrrolidone) (PVP) were plasticized and swollen followed by rapid partitioning of progesterone into the polymer matrix. The as-prepared polystyrene beads incorporated over 10% progesterone by weight while maintaining their initial size and morphological uniformity. Dissolution experiments were also carried out to obtain the release profile of progesterone entrapped within the PVP/PS particles.     

Flexible sorption and transformation behavior in a microporous metal-organic framework

Crystals of the metal-organic framework material Ni(2)(4,4'-bipyridine)(3)(NO(3))(4) (A) have been grown by reaction of Ni(NO(3))(2).6H(2)O and 4,4'-bipyridine in methanol solution. Single-crystal X-ray diffraction experiments show that the ladder structure of the framework is maintained after desolvation of the material, resulting in the production of a porous solid stable to 215(4) degrees C. Powder X-ray diffraction has been employed to confirm the bulk purity and temperature stability of this material. The crystal structure indicates that the pore window has an area of 12.3 A(2). However, sorption experiments show these windows will admit toluene, which has a minimum cross-sectional area of 26.6 A(2), with no significant change in the structure. Monte Carlo docking calculations show that toluene can be accommodated within the large pores of the structure. Exposure of the related microporous material Ni(2)(4,4'-bipyridine)(3)(NO(3))(4).2C(2)H(5)OH (B) to methanol vapor causes a guest-driven solid-state transformation to A which is observed using powder X-ray diffraction. This structural rearrangement proceeds directly from crystalline B to crystalline A and is complete in less than 1 day. Mechanisms for the transformation are proposed which require breaking of at least one in six of the covalent bonds that confer rigidity on the framework.