Direct determination of the complete set of iron normal modes in a porphyrin-imidazole model for carbonmonoxy-heme proteins: [Fe(TPP)(CO)(1-MeIm)

Detailed Fe vibrational spectra have been obtained for the heme model complex [Fe(TPP)(CO)(1-MeIm)] using a new, highly selective and quantitative technique, Nuclear Resonance Vibrational Spectroscopy (NRVS). This spectroscopy measures the complete vibrational density of states for iron atoms, from which normal modes can be calculated via refinement of the force constants. These data and mode assignments can reveal previously undetected vibrations and are useful for validating predictions based on optical spectroscopies and density functional theory, for example. Vibrational modes of the iron porphyrin-imidazole compound [Fe(TPP)(CO)(1-MeIm)] have been determined by refining normal mode calculations to NRVS data obtained at an X-ray synchrotron source. Iron dynamics of this compound, which serves as a useful model for the active site in the six-coordinate heme protein, carbonmonoxy-myoglobin, are discussed in relation to recently determined dynamics of a five-coordinate deoxy-myoglobin model, [Fe(TPP)(2-MeHIm)]. For the first time in a six-coordinate heme system, the iron-imidazole stretch mode has been observed, at 226 cm(-)(1). The heme in-plane modes with large contributions from the nu(42), nu(49), nu(50), and nu(53) modes of the core porphyrin are identified. In general, the iron modes can be attributed to coupling with the porphyrin core, the CO ligand, the imidazole ring, and/or the phenyl rings. Other significant findings are the observation that the porphyrin ring peripheral substituents are strongly coupled to the iron doming mode and that the Fe-C-O tilting and bending modes are related by a negative interaction force constant.     

Near-wall turbulence closure modeling without “damping functions”

An elliptic relaxation model is proposed for the strongly inhomogeneous region near the wall in wall-bounded turbulent shear flow. This model enables the correct kinematic boundary condition to be imposed on the normal component of turbulent intensity. Hence, wall blocking is represented. Means for enforcing the correct boundary conditions on the other components of intensity and on the k — equations are discussed. The present model agrees quite well with direct numerical simulation (DNS) data. The virtue of the present approach is that arbitrary damping functions are not required.     

An anemometer for highly turbulent or recirculating flows

An anemometer which determines flow velocity by ionizing air and sensing the convective displacement of the ions is described. It is suited to measurement in low speed, highly unsteady gas flows. Comparisons to hot wire spectra suggest the corona anemometer has adequate frequency response to make it a useful tool for fluid dynamics measurement.     

Toward consistent formulation of Reynolds stress and scalar flux closures

Langevin stochastic differential equations provide a consistent basis for Reynolds stress, scalar transport and p.d.f. models. However, the stochastic equations must be capable of representing existing closures, like the General Linear Model, or the Rotta and Monin return to isotropy formulations. A consistent approach to derive both Reynolds stress and scalar flux transport equations, starting from a stochastic differential equation for velocity fluctuations, is presented here. A set of algebraic relations for the dispersion tensor is derived for homogeneous shear flow and for the log-layer.     

Vibrational spectroscopy and normal-mode analysis of Fe(II) octaethylporphyrin

The normal-mode spectrum for the four-coordinated heme compound Fe(II) octaethylporphyrin, Fe(OEP), has been determined by refining force constants to the experimental Fe vibrational density of states measured with nuclear resonance vibrational spectroscopy (NRVS). Convergence of the calculated spectrum to the data was achieved by first imposing D4 symmetry on the model structure as well as the force constants, progressively including different internal coordinates of motion, then allowing the true Ci (or S2) point group symmetry of the C(i)1 Fe(OEP) crystal structure. The NRVS-refined normal modes are in good agreement with Raman and IR spectra at high frequencies. Prior density functional theory predictions for a model porphyrin are similar to the core modes computed with the best-fit force field, but significant differences between D4 and Ci modes underline the sensitivity of porphyrin Fe normal modes to structural details. Some differences between the Ci best fit and the NRVS data can be attributed to intermolecular contacts not included in the normal-mode analysis.     

LES of spatially developing turbulent boundary layer over a concave surface

We revisit the problem of a spatially developing turbulent boundary layer over a concave surface. Unlike previous investigations, we simulate the combined effects of streamline curvature as well as curvature-induced pressure gradients on the turbulence. Our focus is on investigating the response of the turbulent boundary layer to the sudden onset of curvature and the destabilising influence of concave surface in the presence of pressure gradients. This is of interest for evaluating the turbulence closure models. At the beginning of the curve, the momentum thickness Reynolds number is 1520 and the ratio of the boundary layer thickness to the radius of curvature is δ₀/R = 0.055. The radial profiles of the mean velocity and turbulence statistics at different locations along the concave surface are presented. Our recently proposed curvature-corrected Reynolds Averaged Navier-Stokes (RANS) model is assessed in an a posteriori sense and the improvements obtained over the base model are reported. From the large Eddy simulation (LES) results, it was found that the maximum influence of concave curvature is on the wall-normal component of the Reynolds stress. The budgets of wall-normal Reynolds stress also confirmed this observation. At the onset of curvature, the effect of adverse pressure gradient is found to be predominant. This decreases the skin friction levels below that in the flat section.     

Catalytic Enantioselective Desymmetrisation as a Tool for the Synthesis of Hodgkinsine and Hodgkinsine B

Two palladium‐catalysed amination protocols are deployed in the desymmetrisation of the complex dimeric alkaloid meso‐chimonanthine. The power of these transformations is showcased in an efficient formal and total synthesis of the natural products hodgkinsine and hodgkinsine B, respectively.