Symmetries in special classes of passive state/signal systems

This article is devoted to a further development of the passive linear continuous time invariant s/s (state/signal) systems theory. The main focus is on the connections between certain symmetry properties (such as reality and reciprocity) of the external characteristics of a s/s system and the respective symmetry of the evolution of the inner state of the system. These connections are investigated for the following classes of passive s/s systems: simple conservative, controllable energy preserving, observable co-energy preserving, optimal, ?-optimal, and minimal balanced, out of which the last three are introduced and studied here for the first time. In each of these six classes a s/s system is defined by its external characteristics up to unitary similarity. Our results are connected with the respective results in the input/state/output systems theory, where the external characteristics of a system are scattering, impedance or transmission matrices.     

Angular-resolved photoelectron spectroscopy of superatom orbitals of fullerenes

Photoelectron angular distributions from both C(60) and C(70) were recorded for low laser intensity femtosecond and picosecond pulses. Rich structure is seen for electron kinetic energies that lie below the photon energy. Strong, broad peaks are observed for photoelectron energies corresponding to single-photon ionization of so-called superatom molecular orbitals (SAMOs). The very simple angular distributions measured for these peaks, the close similarity of the spectra observed from C(60) and C(70), and the comparison with time-dependent density functional theory provide strong support for the SAMO hypothesis.     

Increasing the Affinity of an O-Antigen Polysaccharide Binding Site in Shigella flexneri Bacteriophage Sf6 Tailspike Protein

Broad and unspecific use of antibiotics accelerates spread of resistances. Sensitive and robust pathogen detection is thus important for a more targeted application. Bacteriophages contain a large repertoire of pathogen-binding proteins. These tailspike proteins (TSP) often bind surface glycans and represent a promising design platform for specific pathogen sensors. We analysed bacteriophage Sf6 TSP that recognizes the O-polysaccharide of dysentery-causing Shigella flexneri to develop variants with increased sensitivity for sensor applications. Ligand polyrhamnose backbone conformations were obtained from 2D ¹H,¹H-trNOESY NMR utilizing methine–methine and methine–methyl correlations. They agreed well with conformations obtained from molecular dynamics (MD), validating the method for further predictions. In a set of mutants, MD predicted ligand flexibilities that were in good correlation with binding strength as confirmed on immobilized S. flexneri O-polysaccharide (PS) with surface plasmon resonance. In silico approaches combined with rapid screening on PS surfaces hence provide valuable strategies for TSP-based pathogen sensor design.     

A Full Rank Perfect Code of Length 31

A full rank perfect 1-error correcting binary code of length 31 with a kernel of dimension 21 is described. This was the last open case of the rank-kernel problem of Etzion and Vardy. AMS Classification: 94B25     

Dual‐primal FETI methods for linear elasticity

Dual‐primal FETI methods are nonoverlapping domain decomposition methods where some of the continuity constraints across subdomain boundaries are required to hold throughout the iterations, as in primal iterative substructuring methods, while most of the constraints are enforced by Lagrange multipliers, as in one‐level FETI methods. These methods are used to solve the large algebraic systems of equations that arise in elliptic finite element problems. The purpose of this article is to develop strategies for selecting these constraints, which are enforced throughout the iterations, such that good convergence bounds are obtained that are independent of even large changes in the stiffness of the subdomains across the interface between them. The algorithms are described in terms of a change of basis that has proven to be quite robust in practice. A theoretical analysis is provided for the case of linear elasticity, and condition number bounds are established that are uniform with respect to arbitrarily large jumps in the Young's modulus of the material and otherwise depend only polylogarithmically on the number of unknowns of a single subdomain. The strategies have already proven quite successful in large‐scale implementations of these iterative methods. © 2006 Wiley Periodicals, Inc.     

A Multicontrolled Enamine Configurational Switch Undergoing Dynamic Constitutional Exchange

A multiresponsive enamine‐based molecular switch is presented, in which forward/backward configurational rotation around the C=C bond could be precisely controlled by the addition of an acid/base or metal ions. Fluorescence turn‐on/off effects and large Stokes shifts were observed while regulating the switching process with Cu^II. The enamine functionality furthermore enabled double dynamic regimes, in which configurational switching could operate in conjunction with constitutional enamine exchange of the rotor part. This behavior was used to construct a prototypical dynamic covalent switch system through enamine exchange with primary amines. The dynamic exchange process could be readily turned on/off by regulating the switch status with pH.     

Electron donor-acceptor dyads based on ruthenium(II) bipyridine and terpyridine complexes bound to naphthalenediimide

Two series of photosensitizer-electron acceptor complexes have been synthesized and fully characterized: ruthenium(II) tris(bipyridine) ([Ru(II)(bpy)(2)(bpy-X-NDI)], where X = -CH(2)-, tolylene, or phenylene, bpy is 2,2'-bipyridine, and NDI is naphthalenediimide) and ruthenium(II) bis(terpyridine) ([Ru(II)(Y-tpy)(tpy-X-NDI)], where Y = H or tolyl and X = tolylene or phenylene, and tpy = 2,2':6',2' '-terpyridine). The complexes have been studied by cyclic and differential pulse voltammetry and by steady state and time-resolved absorption and emission techniques. Rates for forward and backward electron transfer have been investigated, following photoexcitation of the ruthenium(II) polypyridine moiety. The terpyridine complexes were only marginally affected by the linked diimide unit, and no electron transfer was observed. In the bipyridine complexes we achieved efficient charge separation. For the complexes containing a phenyl link between the ruthenium(II) and diimide moieties, our results suggest a biphasic forward electron-transfer reaction, in which 20% of the charge-separated state was formed via population of the naphthalenediimide triplet state.     

LIGHT-INDUCED LINEAR ACTION DICHROISM IN PHOTOREVERSIBLY PHOTOCHROMIC SENSOR PIGMENTS—I. THEORY

Abstract— With a photoreversibly photochromic regulator pigment such as phytochrome, linear action dichroism could theoretically be obtained after photoselection even if the molecules are initially randomly oriented: If randomly oriented P_fr (fed-absorbing phytochrome) molecules are partially converted to P_fr (far-red absorbing phytochrome) molecules by plane-polarized red light, those molecules will preferentially be converted which have their 'red' transition moments nearly parallel to the electric vector of the red light. The effect of subsequent plane-polarized far-red light will depend on the plane of polarization. A general theory is developed for how this can be used to determine whether or not the transition moment changes direction during conversion. The pigment need not be isolated, since only physiological reactions (such as germination or chromatic adaptation) are measured.     

Electron donor-acceptor dyads and triads based on tris(bipyridine)ruthenium(II) and benzoquinone: synthesis,characterization, and photoinduced electron transfer reactions

Two electron donor-acceptor triads based on a benzoquinone acceptor linked to a light absorbing [Ru(bpy)(3)](2+) complex have been synthesized. In triad 6 (denoted Ru(II)-BQ-Co(III)), a [Co(bpy)(3)](3+) complex, a potential secondary acceptor, was linked to the quinone. In the other triad, 8 (denoted PTZ-Ru(II)-BQ), a phenothiazine donor was linked to the ruthenium moiety. The corresponding dyads Ru(II)-BQ (4) and PTZ-Ru(II) (9) were prepared for comparison. Upon light excitation in the visible band of the ruthenium moiety, electron transfer to the quinone occurred with a rate constant k(f) = 5 x 10(9) s(-)(1) (tau(f) = 200 ps) in all the quinone containing complexes. Recombination to the ground state followed, with a rate constant k(b) approximately 4.5 x 10(8) s(-)(1) (tau(b) approximately 2.2 ns), for both Ru(II)-BQ and Ru(II)-BQ-Co(III) with no indication of a charge shift to generate the reduced Co(II) moiety. In the PTZ-Ru(II)-BQ triad, however, the initial charge separation was followed by a rapid (k > 5 x 10(9) s(-)(1)) electron transfer from the phenothiazine moiety to give the fairly long-lived PTZ(*)(+)-Ru(II)-BQ(*)(-) state (tau = 80 ns) in unusually high yield for a [Ru(bpy)(3)](2+)-based triad (> 90%), that lies at DeltaG degrees = 1.32 eV relative to the ground state. Unfortunately, this triad turned out to be rather photolabile. Interestingly, coupling between the oxidized PTZ(*)(+) and the BQ(*)(-) moieties seemed to occur. This discouraged further extension to incorporate more redox active units. Finally, in the dyad PTZ-Ru(II) a reversible, near isoergonic electron transfer was observed on excitation. Thus, a quasiequilibrium was established with an observed time constant of 7 ns, with ca. 82% of the population in the PTZ-Ru(II) state and 18% in the PTZ(*)(+)-Ru(II)(bpy(*)(-)) state. These states decayed in parallel with an observed lifetime of 90 ns. The initial electron transfer to form the PTZ(*)(+)-Ru(II)(bpy(*)(-)) state was thus faster than what would have been inferred from the Ru(II) emission decay (tau = 90 ns). This result suggests that reports for related PTZ-Ru(II) and PTZ-Ru(II)-acceptor complexes in the literature might need to be reconsidered.     

An apparatus for the wet ashing of organic matter

An apparatus for the wet ashing of organic material is described. It makes possible the ashing of large quantities of organic matter with pure, ash-free reagents and the determination of various constituents in the samples. This procedure is most useful for the determination of trace elements. It has mainly been used so far for the determination of small amounts of sulfur.