Assignment of conformation-sensitive near-infrared bands in high-spin ferrous haemoproteins. Low-temperature magnetic circular dichroism data

An assignment of the near-infrared bands in the 600–800 nm spectral region observed in magnetic circular dichroism (MCD) spectra of high-spin ferrous haemoproteins is presented. The assignment is based on a relative energy level scheme for iron d-electrons, a comparison of predicted and measured temperature dependences of MCD intensity, a sign of MCD bands and a group theoretical analysis of allowed transitions. The proposed assignment is consistent with the ∼15-nm red shift of the ∼760 nm band on breakage of the Fe-His bond in deoxy-myoglobin at low pH, with low-temperature photolysis experiments available for CO complexes of several haemoproteins. In accordance with the observations, the intensity of the MCD bands for proteins with a sulphur anion of cysteine as proximal haemligand (cytochrome P450 and chloroperoxidase) is predicted to be diminished by at least one order of magnitude compared to that for proteins with an imidazole of a histidine as a protein-derived haemligand (i.e. myoglobin, haemoglobin and horseradish peroxidase). Received: 4 February 1997 / Accepted: 1 May 1997     

Poincaré’s inequalities and Talagrand’s concentration phenomenon for the exponential distribution

Summary. We present a simple proof, based on modified logarithmic Sobolev inequalities, of Talagrand’s concentration inequality for the exponential distribution. We actually observe that every measure satisfying a Poincaré inequality shares the same concentration phenomenon. We also discuss exponential integrability under Poincaré inequalities and its consequence to sharp diameter upper bounds on spectral gaps. Received: 10 June 1996 / In revised form: 9 August 1996     

Time-resolved synchrotron X-ray study of crystalline phase transition in poly(aryl ether ketone ketone) containing alternated terephthalic/isophthalic moieties

Unique crystallization and melting behavior in poly(aryl ether ketone ketone) containing alternated terephthalic and isophthalic moieties were studied by time-resolved synchrotron x-ray methods. Recently, this material has been shown to exhibit three polymorphs (forms I, II, and III). In this work, we further investigated their distinctive thermal properties and found that form I is the dominating and the most thermally stable phase while form II is favored by fast nucleation conditions and is the least stable phase. On the other hand, form III represents a minor intermediate phase that usually coexists with form I and can be transferred from form II and to form I. Structural and morphological changes in form I have been followed by simultaneous wide-angle x-ray diffraction (WAXD)/small-angle x-ray scattering (SAXS) measurements during cold- or melt-crystallization and subsequent melting. In all cases, a larger dimensional change was found in the crystallographic a-axis than the b-axis during heating and cooling. This may be due to the greater lateral stress variation with respect to temperature along the a direction of the primary lamellae which is induced by either the formation of secondary lamellae or the preferential chain-folding direction in poly(aryl ether ketone ketone)s. During the phase transitions of form II ← III in the cold-crystallized specimen and form III ← I in the melt-crystallized samples, lamellar variables (long period, lamellar thickness, and invariant) obtained from SAXS remain almost constant. This indicates that the density distribution in the long spacing is independent of the melting in form II or III. For melt-crystallization, the corresponding changes in unit-cell dimensions and lamellar morphology during the annealing-induced low endotherm are most consistent with the argument that these changes are due to the melting of thin lamellar population. © 1995 John Wiley & Sons, Inc.     

Barium ferrite particulates prepared by a salt-melt method

Barium ferrite particulates have been prepared by coprecipitation and calcination in a flux of NaCl-KCl. It was found that a flux containing more than 30 wt% KCl tends to seriously deteriorate the magnetic properties of resultant perticulates. The flux with 10 wt% KCl or less showed promising results. A Ba(CoZr)_0.75Fe_10.5O₁₉ particulate showed the best properties, i.e., a saturation magnetization of 68.5, a squareness ratio of 0.49, and a coercivity of 1280 Oe, when calcined in NaCl at 900°C for 4 h.     

Variations of constants and red-shift in 6D cosmology

On the basis of the general class of solutions of 6D vacuum Einstein equations and using well-known results of the 6D geometric model of electroweak and gravitational interactions, the variations of fundamental physical constants and their influence on the observed red-shift of galaxies are investigated. By considering the interpretation of extra components of the 6D metric as reproducing the properties of matter in the 4D curved space-time, the effective quantities of matter are obtained. In particular, the states of dust and radiation are shown. The corresponding 5D models were also investigated.     

Unreasonable effectiveness of symmetry in physics

We prove that in some reasonable sense, every possible physical law can be reformulated in terms of symmetries. This result explains the well-known success of the group-theoretic approach in physics.     

Effects of strong coupling in homonuclear correlation spectroscopy

A calculation of the complex signals in homonuclear correlation spectra (HOMCOR) of strongly coupled ABX three-spin systems is presented. It is shown that the presence of strong coupling causes the behavior of the cross-peaks to differ significantly from that found in the case of weak coupling. Two classes of connectivity patterns, namely weak and strong connectivity pairs of transitions are distinguished. Closed expressions for the real amplitudes are given. The dependence of the real amplitude on the flip angle of the mixing pulse and on the coupling strength is analyzed.     

Semi-parametric estimation of covariate effects using the positive stable frailty model

Many biological and medical studies have as a response of interest the time to occurrence of some event, such as the occurrence of a particular symptom or disease, remission, relapse, death due to some specific disease, or simply death. In this paper we study the problem of assessing the effect of potential risk factors on the outcome event of interest through a parametric or semi-parametric frailty model where the lifetimes have a reason to be considered dependent. This dependence may arise because of multiple endpoints within the same individual or because, when studying a single endpoint, there are natural groupings between study subjects. The objective of this paper is to extend both parametric and semi-parametric approaches to regression analysis in which the lifetimes of individuals in a group are effected by the same random frailty which follows a positive stable distribution. Some comparisons of the properties of this frailty distribution with other frailty distributions are made and an example which assesses the effect of a treatment in a litter-matched tumorigenesis study is presented.