Characterization of low-energy chlorophylls in the PSI-LHCI supercomplex from Chlamydomonas reinhardtii. A site-selective fluorescence study

Almost all photosystem I (PSI) complexes from oxygenic photosynthetic organisms contain chlorophylls that absorb at longer wavelength than that of the primary electron donor P700. We demonstrate here that the low-energy pool of chlorophylls in the PSI-LHCI complex from the green alga Chlamydomonas reinhardtii, containing five to six pigments, is significantly blue-shifted (A(max) at 700 nm at 4 K) compared to that in the PSI core preparations from several species of cyanobacteria and in PSI-LHCI particles from higher plants. This makes them almost isoenergetic with the primary donor. However, they keep the other characteristic features of "red" chlorophylls: clear spectral separation from the bulk chlorophylls, big Stokes shift revealing pronounced electron-phonon coupling, and large homogeneous and inhomogeneous broadening of approximately 170 and approximately 310 cm(-1), respectively.     

Methylene‐Bridged Metallocenes with 2,2′‐Methylenebis[1H‐inden‐1‐yl] Ligands: Synthesis,Characterization, and Polymerization Catalysis of a Synthetically Simple Class of C2‐ and C2v‐Symmetric ansa‐Metallocenes

The acid‐catalyzed reaction between formaldehyde and 1H‐indene, 3‐alkyl‐ and 3‐aryl‐1H‐indenes, and six‐membered‐ring substituted 1H‐indenes, with the 1H‐indene/CH₂O ratio of 2 : 1, at temperatures above 60° in hydrocarbon solvents, yields 2,2′‐methylenebis[1H‐indenes] 1 – 8 in 50–100% yield. These 2,2′‐methylenebis[1H‐indenes] are easily deprotonated by 2 equiv. of BuLi or MeLi to yield the corresponding dilithium salts, which are efficiently converted into ansa‐metallocenes of Zr and Hf. The unsubstituted dichloro{(1,1′,2,2′,3,3′,3a,3′a,7a,7′a‐η)‐2,2′‐methylenebis[1H‐inden‐1‐yl]}zirconium ([ZrCl₂( 1′ )]) is the least soluble in organic solvents. Substitution of the 1H‐indenyl moieties by hydrocarbyl substituents increases the hydrocarbon solubility of the complexes, and the presence of a substituent larger than a Me group at the 1,1′ positions of the ligand imparts a high diastereoselectivity to the metallation step, since only the racemic isomers are obtained. Methylene‐bridged ‘ansa‐zirconocenes’ show a noticeable open arrangement of the bis[1H‐inden‐1‐yl] moiety, as measured by the angle between the planes defined by the two π‐ligands (the ‘bite angle’). In particular, of the ‘zirconocenes’ structurally characterized so far, the dichloro{(1,1′,2,2′,3,3′,3a,3′a,7a,7′a‐η)‐2,2′‐methylenebis[4,7‐dimethyl‐1H‐inden‐1‐yl]}zirconium ([ZrCl₂( 5′ )] is the most open. The mixture [ZrCl₂( 1′ )]/methylalumoxane (MAO) is inactive in the polymerization of both ethylene and propylene, while the metallocenes with substituted indenyl ligands polymerize propylene to atactic polypropylene of a molecular mass that depends on the size of the alkyl or aryl groups at the 1,1′ positions of the ligand. Ethene is polymerized by rac‐dichloro{(1,1′,2,2′,3,3′,3a,3′a,7a,7′a‐η)‐2,2′‐methylenebis[1‐methyl‐1H‐inden‐1‐yl]}zirconium ([ZrCl₂( 2′ )])/MAO to polyethylene waxes (average degree of polymerization ca. 100), which are terminated almost exclusively by ethenyl end groups. Polyethylene with a high molecular mass could be obtained by increasing the size of the 1‐alkyl substituent.     

Stereospecific Cyclopolymerization with Group 4 Metallocenes

Homogeneous Ziegler-Natta catalysts are stereoselective cyclopolymerization catalysts for non-conjugated dienes. Cyclopolymerization of 1,5-hexadiene affords poly(methylene-l,3-cyclopentane) (PMCP), a polymer for which four structures of maximum order are possible. A variety of metallocene catalyst precursors have been investigated; the molecular weight and microstructure of the polymers are sensitive to the structure of the catalyst precursor as well as the reaction conditions. The selectivity for cyclization depends on reaction conditions; decreasing the olefin concentration and increasing the temperature of the reaction favor cyclization. The stereochemistry of cyclopolymers can also be controlled with appropriate choice of catalyst precursor. Diastereoselective cyclopolymerization of 1,5-hexadiene with achiral catalysts yields atactic trans-PMCP and cis-PMCP, depending on the catalyst precursor. Enantioselective cyclopolymerization with optically active catalysts yields optically active poly(methylenecyclopentane), a novel example of a polymer which is chiral by virtue of its main-chain stereochemistry.     

Confinement and orientational study at liquid crystal phase transitions

Abstract

We have studied the heat capacity of the thermotropic liquid crystal, octylcyanobiphenyl (8CB), confined to the nearly cylindrical, 0·2 μm diameter pores of Anopore membranes. Orientation of the nematic director within the pores can be controlled with surface treatment. It is known from NMR measurements that the nematic director is aligned parallel to the pore axis in the untreated membrane. A perpendicular alignment is obtained when the pore surface is treated with lecithin. The second order smectic A to nematic (S_A–N) and the weakly first order nematic to isotropic (N–I) phase transitions of 8CB were studied in these pores, for both director orientations, using an AC calorimetry technique. Effects on heat capacity amplitudes, transition temperature shifts, rounding and broadening of these phase transitions will be presented and contrasted with bulk measurements.     

A hybrid DFT description of the (0001) surface of americium-I

Using a periodic slab model for the (0001) surface of americium-I (Am-I) and the full-potential linear augmented plane wave (FP-LAPW) plus local basis implementation of hybrid density functional theory (HYB-DFT), we show that with a fraction of 0.40 Hartree-Fock (HF) exchange, the non-magnetic nature of the Am-I surface is well described and the electronic properties are in good agreement with recent photoemission spectroscopy data. The work function and surface energy of the non-magnetic semi-infinite surface are predicted to 3.46 eV and 1.03 J/m², respectively. As a function of slab thickness, the surface properties, namely the surface energy, work function, and slab incremental energy converge after five layers. A five layer slab is thus deemed to be sufficient to very accurately model the adsorption of impurities on the surface and adsorbate-induced changes in the work function. A layer-by-layer examination of the nine-layer non-magnetic slab clearly indicates that the 5f electrons are uniformly localized, that is, the 5f electron localization is independent of the position of the layer.     

Space distribution of harmonic mode vibration amplitudes in nonlinear finite piezoelectric transducer

Nonlinear elastic vibrations of cylindrical piezoelectric transducers are investigated both experimentally and theoretically. A particular behaviour, that relates the space distribution of the fundamental mode vibration to those of the second and third harmonic components, is observed. A simplified physical interpretation of the phenomenon is given.     

Non-Deterministic Closure Theory and Universal Arrows

Traditional closure theory discusses the closure operations on orders with graph-theoretic methods, or the reflectors on skeletal categories with category-theoretic methods. Both approaches are confined, like most of classical mathematics, to total and deterministic operations. So traditional closure theory makes it possible to define the semantics of the while-do commands only for terminating and deterministic programming. This paper outlines a closure theory for relations which transcend totality and determinism. For the sake of conciseness, the language used is that of graph theory but the methods are category-theoretic and some hints are offered for a possible translation into the language of category theory. Our basic idea is that closure relations consist of universal arrows in the sense of category theory. The new closure theory is appropriate for defining a semantics of the while-do commands both for terminating, deterministic programming and for non-terminating, non-deterministic programming.     

Monomiality and partial differential equations

We show that the combination of the formalism underlying the principle of monomiality and of methods of an algebraic nature allows the solution of different families of partial differential equations. Here we use different realizations of the Heisenberg–Weyl algebra and show that a Sheffer type realization leads to the extension of the method to finite difference and integro-differential equations.     

1H and 13C NMR analysis of 2‐acetamido‐3‐mercapto‐3‐methyl‐N‐aryl‐butanamides and 2‐acetamido‐3‐methyl‐3‐nitrososulfanyl‐N‐aryl‐butanamide derivatives

The complete assignment of the ¹H and ¹³C NMR spectra of various 2‐acetamido‐3‐mercapto‐3‐methyl‐N‐aryl‐butanamides and 2‐acetamide‐3‐methyl‐3‐nitrososulfanyl‐N‐aryl‐butanamides with p‐methoxy, o‐chloro and m‐chloro substituents is reported. Copyright © 2013 John Wiley & Sons, Ltd.