Mechanistic study into the direct epoxidation of propene over gold/titania catalysts

The epoxidation of propene over gold/titania based catalysts was investigated using different techniques. Infrared spectroscopic information showed that one key step in the reaction mechanism is a reaction catalyzed by gold between titania surface groups and propene. In this reaction step, a bidentate propoxy species is formed on titania. This species adsorbs strongly on the catalyst, and it is the same species which is formed when propene oxide adsorbs on titania. Gravimetrical adsorption experiments and catalytic tests show that product adsorption and desorption are important factors determining the catalytic activity and the catalyst stability. By combining the information from different techniques, a kinetic mechanism is proposed.     

Axial and equatorial ligand effects on biomimetic cysteine dioxygenase model complexes

Density functional theory (DFT) calculations are presented on biomimetic model complexes of cysteine dioxygenase and focus on the effect of axial and equatorial ligand placement. Recent studies by one of us [Y. M. Badiei, M. A. Siegler and D. P. Goldberg, J. Am. Chem. Soc. 2011, 133, 1274] gave evidence of a nonheme iron biomimetic model of cysteine dioxygenase using an i-propyl-bis(imino)pyridine, equatorial tridentate ligand. Addition of thiophenol, an anion - either chloride or triflate - and molecular oxygen, led to several possible stereoisomers of this cysteine dioxygenase biomimetic complex. Moreover, large differences in reactivity using chloride as compared to triflate as the binding anion were observed. Here we present a series of DFT calculations on the origin of these reactivity differences and show that it is caused by the preference of coordination site of anion versus thiophenol binding to the chemical system. Thus, stereochemical interactions of triflate and the bulky iso-propyl substituents of the ligand prevent binding of thiophenol in the trans position using triflate. By contrast, smaller anions, such as chloride, can bind in either cis or trans ligand positions and give isomers with similar stability. Our calculations help to explain the observance of thiophenol dioxygenation by this biomimetic system and gives details of the reactivity differences of ligated chloride versus triflate.     

Origin of the Correlation of the Rate Constant of Substrate Hydroxylation by Nonheme Iron(IV)–oxo Complexes with the Bond‐Dissociation Energy of the C?H Bond of the Substrate

A series of hydrogen‐abstraction barriers of a nonheme iron(IV)–oxo oxidant mimicking the active species of taurine/α‐ketoglutarate dioxygenase (TauD) are rationalized by using a valence‐bond curve‐crossing diagram (see figure). It is shown that the barriers correlate with the strength of the C? H bond. Furthermore, electronic differences explain the differences between nonheme and heme iron(IV)–oxo hydrogen‐abstraction barriers.

     

Uranyl coordination environment in hydrophobic ionic liquids: an in situ investigation

Different inner-sphere coordination environments are observed for the uranyl nitrate complexes formed with octyl-phenyl-N,N-diisobutylcarbamoylmethylphosphine oxide and tributyl phosphate in dodecane and in the hydrophobic ionic liquids (ILs) [C(4)mim][PF(6)] and [C(8)mim][N(SO(2)CF(3))(2)]. Qualitative differences in the coordination environment of the extracted uranyl species are implied by changes in peak intensity patterns and locations for uranyl UV-visible spectral bands when the solvent is changed. EXAFS data for uranyl complexes in dodecane solutions is consistent with hexagonal bipyramidal coordination and the existence of UO(2)(NO(3))(2)(CMPO)(2). In contrast, the complexes formed when uranyl is transferred from aqueous nitric acid solutions into the ILs exhibit an average equatorial coordination number of approximately 4.5. Liquid/liquid extraction results for uranyl in both ILs indicate a net stoichiometry of UO(2)(NO(3))(CMPO)(+). The concentration of the IL cation in the aqueous phase increases in proportion to the amount of UO(2)(NO(3))(CMPO)(+) in the IL phase, supporting a predominantly cation exchange mechanism for partitioning in the IL systems.     

Cryotrapping gas chromatography-Fourier transform infrared spectrometry in environmental analysis: A pilot study

The potential applicability of cryotrapping gas chromatography-Fourier transform infrared spectrometry in environmental analysis was studied. First results of on-the-flight measurements on pesticides and polynuclear aromatic hydrocarbons show detection limits in the 100–500 pg range. The low-temperature spectra obtained appear to be closely comparable to conventionally recorded spectra. Library search procedures based on existing solid-phase spectra appear to be useful.     

Single-photon ionisation of TMPD in liquid CCl4 observed by time-resolved microwave conductivity

A large microwave conductivity change is observed on laser flash photolysis (308 nm) of a solution of TMPD in CCl₄. This is ascribed to single-photon ionisation of the solute resulting in the formation of a stable TMPD⁺Cl^? ion pair. The dipole moment of the ion pair is estimated to be (8.7 ± 0.9)(φ*)^{?$\text{1}\text{2}$} where φ* is the quantum efficiency for ion-pair formation.     

Riemannian geometry of irrotational vortex acoustics

We consider acoustic propagation in an irrotational vortex, using the technical machinery of differential geometry to investigate the "acoustic geometry" that is probed by the sound waves. The acoustic space-time curvature of a constant circulation hydrodynamical vortex leads to deflection of phonons at appreciable distances from the vortex core. The scattering angle for phonon rays is shown to be quadratic in the small quantity Gamma/2pi(cb), where Gamma is the vortex circulation, c the speed of sound, and b the impact parameter.     

Antigen-antibody interactions: binding studies with fluorescence and surface plasmon resonance exemplified by acid-traseolide as antigen

The interaction between the musk fragrance acid-traseolide and monoclonal antibodies (mAB) generated against this odorant has been investigated with two different techniques. Fluorescence spectroscopy was used to study the quenching of tryptophan fluorescence of the antibody upon binding acid-traseolide. This spectroscopic approach is based on measurements under equilibrium conditions. The second technique exploited the surface plasmon resonance (SPR) phenomenon. The acid-traseolide was immobilized in the surface matrix and upon presenting mAB changes in SPR were recorded in real time during the association reaction. The SPR approach can be considered as a kinetic method. Although having a different origin, both methods lead to comparable equilibrium dissociation constants (Kd). However, the results obtained with fluorescence spectroscopy were more accurate and reproducible. Not only the association of acid-traseolide with antibody was evaluated, also Fab fragment and peptide (H3-peptide) mimicking the heavy chain CDR3 of this antibody were included in this study. The Kd-values, determined by both methods, increase in the order mAB < Fab < H3-peptide because of diminishing recognition.     

Investigation on the feasibility of using an Ulbricht sphere for the absolute calibration of an ICP or other source at specific wavelengths

The short term and long term stability of an Ulbricht sphere was investigated by comparing its radiation at four Balmer wavelengths with those of two Sylvania projector lamps. A slight positive trend in the radiation intensity of the Ulbricht sphere was observed. This was attributed to a change in the molecular structure of the paint used to cover the inside of the sphere. However, the radiance varied less than 3% for 14 h burning time. The uncertainty in the primary calibration of the Tungsten standard lamp was given as ±3% in the wavelength range 400–600 nm. It was hence concluded that the sphere is suitable for spectral calibration purposes for a period of 14 h operational time without being recalibrated.