Functional mimic of dioxygen-activating centers in non-heme diiron enzymes: mechanistic implications of paramagnetic intermediates in the reactions between diiron(II) complexes and dioxygen

Two tetracarboxylate diiron(II) complexes, [Fe(2)(mu-O(2)CAr(Tol))(2)(O(2)CAr(Tol))(2)(C(5)H(5)N)(2)] (1a) and [Fe(2)(mu-O(2)CAr(Tol))(4)(4-(t)BuC(5)H(4)N)(2)] (2a), where Ar(Tol)CO(2)(-) = 2,6-di(p-tolyl)benzoate, react with O(2) in CH(2)Cl(2) at -78 degrees C to afford dark green intermediates 1b (lambda(max) congruent with 660 nm; epsilon = 1600 M(-1) cm(-1)) and 2b (lambda(max) congruent with 670 nm; epsilon = 1700 M(-1) cm(-1)), respectively. Upon warming to room temperature, the solutions turn yellow, ultimately converting to isolable diiron(III) compounds [Fe(2)(mu-OH)(2)(mu-O(2)CAr(Tol))(2)(O(2)CAr(Tol))(2)L(2)] (L = C(5)H(5)N (1c), 4-(t)BuC(5)H(4)N (2c)). EPR and M?ssbauer spectroscopic studies revealed the presence of equimolar amounts of valence-delocalized Fe(II)Fe(III) and valence-trapped Fe(III)Fe(IV) species as major components of solution 2b. The spectroscopic and reactivity properties of the Fe(III)Fe(IV) species are similar to those of the intermediate X in the RNR-R2 catalytic cycle. EPR kinetic studies revealed that the processes leading to the formation of these two distinctive paramagnetic components are coupled to one another. A mechanism for this reaction is proposed and compared with those of other synthetic and biological systems, in which electron transfer occurs from a low-valent starting material to putative high-valent dioxygen adduct(s).     

A partition function algorithm for nucleic acid secondary structure including pseudoknots

Nucleic acid secondary structure models usually exclude pseudoknots due to the difficulty of treating these nonnested structures efficiently in structure prediction and partition function algorithms. Here, the standard secondary structure energy model is extended to include the most physically relevant pseudoknots. We describe an O(N(5)) dynamic programming algorithm, where N is the length of the strand, for computing the partition function and minimum energy structure over this class of secondary structures. Hence, it is possible to determine the probability of sampling the lowest energy structure, or any other structure of particular interest. This capability motivates the use of the partition function for the design of DNA or RNA molecules for bioengineering applications.     

Zement

Ohne Zusammenfassung     

Chapter 4:algebraic sets, polynomials, and other functions

Let T be a linear operator on the vector space V ofn×n matrices over a field F. We discuss two types of problems in this chapter. First, what can we say about T if we assume that T maps a given algebraic set such as the special linear group into itself? Second, let p(x) be a polynomial function (such as det) on V into F. What can we say about T if Tpreserves p(x), i.e. p(T(X)) = p(X) for all X in V?     

Comment on "Optical-fiber-based Mueller optical coherence tomography"

We comment on the recent Letter by Jiao et al. [Opt. Lett. 28, 1206 (2003)] in which a polarization-sensitive optical coherence tomography system was presented. Interrogating a sample with two orthogonal incident polarization states cannot always recover birefringence correctly. A previously presented fiber-based polarization-sensitive system was inaccurately characterized, and its method of eliminating the polarization distortion caused by single-mode optical fiber was presented earlier by Saxer et al. [Opt. Lett. 25, 1355 (2000)].     

Optic axis determination accuracy for fiber-based polarization-sensitive optical coherence tomography

We present a generalized analysis of fiber-based polarization-sensitive optical coherence tomography with an emphasis on determination of sample optic axis orientation. The polarization properties of a fiber-based system can cause an overall rotation in a Poincaré sphere representation such that the plane of possible measured sample optic axes for linear birefringence and diattenuation no longer lies in the QU-plane. The optic axis orientation can be recovered as an angle on this rotated plane, subject to an offset and overall indeterminacy in sign such that only the magnitude, but not the direction, of a change in orientation can be determined. We discuss the accuracy of optic axis determination due to a fundamental limit on the accuracy with which a polarization state can be determined as a function of signal-to-noise ratio.     

Congratulations to Akusticheskii Zhurnal on the occasion of its 50th anniversary. Vibrations of spherical inclusions in elastic solids

Variational principles are derived for the analysis of dynamical phenomena associated with spherical inclusions embedded in homogeneous isotropic elastic solids. The starting point is Hamilton’s principle, with the material properties assumed to vary only with the radial distance r from the origin. Attention is restricted to disturbances that are symmetric about the polar (z) axis, such that the nonzero displacement components in spherical coordinates, u _r and u_θ, are independent of the polar coordinate φ. The symmetry allows for a decoupling of the polar components, the nth of which is described by U _{r, n} (r, t)P _n (cosθ) and U_{θ, n}(r, t)dP _n /dθ. A variational principle is subsequently derived for the field quantities U _{r, n} and U_{θ, n}. Concepts analogous to those of the theory of matched asymptotic expansions are used to embellish the principle in order to allow for the damping associated with the outward radiation of elastic waves. Examples illustrating the use of the variational principle for formulating plausible lumped-parameter models are given for the cases of n = 0 and n = 1.