Orientational relaxation of pheophorbide-a molecules in the ground and in the first excited state measured by transient dichroism spectroscopy

We report on transient dichroism spectroscopy carried out on pheophorbide-a in ethanol to measure the response time of the pump-beam induced anisotropy after selective excitation at high excitation levels. From the observed time behaviors of induced absorption, transient amplification, and of the bleaching signal, the orientational relaxation times of pheophorbide-a in the first excited singlet state and in the ground state were obtained separately to be 370 and 250 ps, respectively. It is found that pheophorbide-a behaves like a spherical rotor in the first excited state, while in the ground state randomization of molecules is dominated by the rotation around its quasi-symmetry axis. Because of rotation free measurement of ordinary transient absorption spectra fail in the case of ground state depletion, the observed orientational relaxation time of the ground state have to be taken into account to fit the bleaching kinetics obtained from transient absorption spectra very well to determine the intersystem crossing yield of pheophorbide-a to be 0.46.     

Porous polycrystals built up by uniformly and axisymmetrically oriented needles: homogenization of elastic propertiesPolycristaux poreux constitués d'aiguilles orientées de façon uniforme ou axisymétrique : homogénéisation des propriétés élastiques

Porous polycrystal-type microstructures built up of needle-like platelets or sheets are characteristic for a number of biological and man-made materials. Herein, we consider (i) uniform, (ii) axisymmetrical orientation distribution of linear elastic, isotropic as well as anisotropic needles. Axisymmetrical needle orientation requires derivation of the Hill tensor for arbitrarily oriented ellipsoidal inclusions with one axis tending towards infinity, embedded in a transversely isotropic matrix; therefore, Laws' integral expression of the Hill tensor is evaluated employing the theory of rational functions. For a porosity lower 0.4, the elastic properties of the polycrystal with uniformly oriented needles are quasi-identical to those of a polycrystal with solid spheres. However, as opposed to the sphere-based model, the needle-based model does not predict a percolation threshold. As regards axisymmetrical orientation distribution of needles, two effects are remarkable: Firstly, the sharper the cone of orientations the higher the anisotropy of the polycrystal. Secondly, for a given cone, the anisotropy increases with the porosity. Estimates for the polycrystal stiffness are hardly influenced by the anisotropy of the bone mineral needles. Our results also confirm the very high degree of orientation randomness of crystals building up mineral foams in bone tissues. To cite this article: A. Fritsch et al., C. R. Mecanique 334 (2006).     

Overcoming apparent susceptibility-induced anisotropy (aSIA) by bipolar double-pulsed-field-gradient NMR

Double-Pulsed-Field-Gradient (d-PFG) MR is emerging as a powerful new means for obtaining unique microstructural information in opaque porous systems that cannot be obtained by conventional single-PFG (s-PFG) methods. The angular d-PFG MR methodology is particularly important since it can utilize the effects of microscopic anisotropy (μA) and compartment shape anisotropy (csA) in the E(ψ) profile at the different t_m regimes to provide detailed information on compartment size and eccentricity. An underlying assumption is that the PFGs that are imparted to weigh diffusion are the only gradients present; however, in realistic systems and especially where there are randomly oriented anisotropic pores, susceptibility effects may induce strong internal gradients. In this study, the effects of such internal gradients on E(ψ) plots obtained from angular d-PFG MR and on microstructural information that can be obtained from s-PFG and d-PFG MR were investigated. First, it was found that internal gradients induce a bias in the s-PFG MR results, thus creating an anisotropy that is not related to microstructure, termed apparent-Susceptibility-Induced-Anisotropy (aSIA). We then show that aSIA effects are also manifest in different ways in the angular d-PFG MR experiment in controlled phantoms and in realistic systems such as quartz sand, emulsions, and biological systems. The effects of aSIA in some cases completely masked the effects of μA and csA; however, we subsequently show that by introducing bipolar gradients to the d-PFG MR (bp-d-PFG), the effects of aSIA can be largely suppressed, restoring the E(ψ) plots that are expected from the theory along with the microstructural information that it conveys. We conclude that when specimens are characterized by strong internal gradients, the novel information on μA and csA that is manifest in the E(ψ) plots can indeed be inferred when bp-d-PFG MR is used, i.e. when bipolar gradients are applied.     

Optical properties of superhard BC5: First-principles calculations

BC₅ is a newly synthesized superhard material. We present a systematic investigation of optical properties of BC₅ in P3m1 and I-4m2 phases at ambient and high pressure in the framework of density functional theory with the generalized gradient approximation (GGA) in this paper. Optical properties such as dielectric function, refractive index, absorption, reflectivity and electron energy-loss spectrum are obtained successfully. The feature in the spectra of the optical parameters is discussed. Through calculation, we find BC₅ is optically anisotropic. Moreover, the dielectric function exhibits a large change at 70 GPa pressure for P3m1 BC₅ phase, but I-4m2 phase not, indicating the stable electronic structure that the I-4m2 phase possesses.     

The use of stress for the control of magnetic anisotropy in amorphous FeSiBC thin films: a magneto-optic study

Magnetostrictive FeSiBC amorphous thin films based on the METGLAS^® 2605SC composition have been produced by RF magnetron sputtering. The magnetic properties were investigated using the magneto-optical Kerr effect, with both point hysteresis measurements and domain imaging. Significant in-plane anisotropy is observed in the as-grown samples, which was attributed to the residual field from the magnetron sputter source. The effects of various treatments on the samples were investigated, including the use of forming fields, stress, and thermal processing. The deliberate introduction of stress into these materials is found to allow excellent control of both the direction and magnitude of magnetic anisotropy, and can also be used as a novel method for the absolute measurement of magnetostriction. The treatments are evaluated for their potential to control anisotropy in magnetostrictive device applications.     

Singularities in a Solution to a Rotating Orthotropic Disk with Temperature Gradient

A semi-analytical solution is obtained for a rotating stress-free edge disk of constant thickness and density. In the plastic range, the Hill’s quadratic orthotropic yield criterion is adopted. In the elastic range, the Hooke’s law holds with thermal effects included. The analysis of singularities performed may be used for correct implementation of numerical codes and preliminary engineering design.     

A note on the extensional viscosity of elastic liquids under strong flows

In this article a parametric study based on a balance between viscous drag and restoring Brownian forces is used in order to construct a nonlinear dumbbell model with a finite spring and a drag correction for a dilute polymer solution. The constitutive equations used are reasonable approximation for describing flows of very dilute polymer solutions such as those used in turbulent drag reduction. We investigate the response of an elastic liquid under extensional flows in order to explore the roles of a stress anisotropy and of elasticity in strong flows. It is found that for low Reynolds numbers, the extensional viscosity of a dilute polymer solution is governed by two parameters: a Deborah number representing the importance of the elasticity on the flow and the macromolecule extensibility that accounts for the viscous anisotropic effects caused by the macromolecule orientation. Two different asymptotic regimes are described.The first corresponds to an elastic limit in which the extensional viscosity is a function of the Deborah number and the particle volume fraction. The second is an anisotropic regime with the extensional viscosity independent of Deborah number but strongly dependent on macromolecule aspect ratio. The analysis may explain from a phenomenological point of view why few ppms of macromolecules of high molecule weight or a small volume fraction of long fibres produce important attenuation of the pressure drop in turbulent flows. On the basis of our analysis it is seen that the anisotropic limit of the extensional viscosity caused by extended polymers under strong flows should play a key role in the attenuation of flow instability and in the mechanism of drag reduction by polymer additives.     

Evolution of material voids for highly anisotropic surface energy

In this paper we consider the evolution by surface diffusion of material voids in a linearly elastic solid, focusing on the evolution of voids with large surface energy anisotropy. It is well known that models for the time evolution of similar material surfaces can become mathematically ill-posed when the surface energy is highly anisotropic. In some cases, this ill-posedness has been associated with the formation of corners along the interface. Here the ill-posedness is removed through a regularization which incorporates higher order terms in the surface energy. Spectrally accurate numerical simulations are performed to calculate the steady-state solution branches and time-dependent evolution of voids, with a particular emphasis on inferring trends in the zero regularization (c→0) limit. For steady voids with large anisotropy we find that apparent corners form as c→0. In the presence of elastic stresses σ the limiting corner angles are most often found to differ from angles found on the (σ=0) Wulff shape. For large elastic stresses we find that steady solutions no longer exist; instead the void steadily lengthens via a filamenting instability referred to as tip streaming.     

Anisotropy resolved multidimensional emission spectroscopy (ARMES): A new tool for protein analysis

Structural analysis of proteins using the emission of intrinsic fluorophores is complicated by spectral overlap. Anisotropy resolved multidimensional emission spectroscopy (ARMES) overcame the overlap problem by the use of anisotropy, with chemometric analysis, to better resolve emission from different fluorophores. Total synchronous fluorescence scan (TSFS) provided information about all the fluorophores that contributed to emission while anisotropy provided information about the environment of each fluorophore. Here the utility of ARMES was demonstrated via study of the chemical and thermal denaturation of human serum albumin (HSA).