FTIR spectra and normal-mode analysis of a tetranuclear manganese adamantane-like complex in two electrochemically prepared oxidation states: relevance to the oxygen-evolving complex of photosystem II

The IR spectra and normal-mode analysis of the adamantane-like compound [Mn(4)O(6)(bpea)(4)](n+) (bpea = N,N-bis(2-pyridylmethyl)ethylamine) in two oxidation states, Mn(IV)(4) and Mn(III)Mn(IV)(3), that are relevant to the oxygen-evolving complex of photosystem II are presented. Mn-O vibrational modes are identified with isotopic exchange, (16)O-->(18)O, of the mono-micro-oxo bridging atoms in the complex. IR spectra of the Mn(III)Mn(IV)(3) species are obtained by electrochemical reduction of the Mn(IV)(4) species using a spectroelectrochemical cell, based on attenuated total reflection [Visser, H.; et al. Anal. Chem. 2001, 73, 4374-4378]. A novel method of subtraction is used to reduce background contributions from solvent and ligand modes, and the difference and double-difference spectra are used in identifying Mn-O bridging modes that are sensitive to oxidation state change. Two strong IR bands are observed for the Mn(IV)(4) species at 745 and 707 cm(-1), and a weaker band is observed at 510 cm(-1). Upon reduction, the Mn(III)Mn(IV)(3) species exhibits two strong IR bands at 745 and 680 cm(-1), and several weaker bands are observed in the 510-425 cm(-1) range. A normal-mode analysis is performed to assign all the relevant bridging modes in the oxidized Mn(IV)(4) and reduced Mn(III)Mn(IV)(3) species. The calculated force constants for the Mn(IV)(4) species are f(r)(IV)= 3.15 mdyn/A, f(rOr) = 0.55 mdyn/A, and f(rMnr) = 0.20 mdyn/A. The force constants for the Mn(III)Mn(IV)(3) species are f(r)(IV)= 3.10 mdyn/A, f(r)(III)= 2.45 mdyn/A, f(rOr) = 0.40 mdyn/A, and f(rMnr) = 0.15 mdyn/A. This study provides insights for the identification of Mn-O modes in the IR spectra of the photosynthetic oxygen-evolving complex during its catalytic cycle.     

Demonstration of improved beam quality in an image-rotating optical parametric oscillator

We performed laboratory and numerical modeling studies of an optical parametric oscillator with 90 degrees intracavity image rotation. We found that the signal beam was more symmetric than that from comparable cavities without image rotation, and it had low values of the beam quality factor, M(2) . Oscillator performance agreed well with our numerical model.     

Numerical investigation of a developmental pneumatically fed impact pulveriser

The current work has been carried out on a pneumatically fed impact pulveriser. A recent build of the proposed device, and early experiments have shown promising size reduction ratios and energy savings in comparison with conventional milling techniques.     

Implementation and analysis of a variant of the dual method for the capacitated transshipment problem

This paper presents a variant of the dual simplex method for the capacitated pure network problem and a computational analysis of this algorithm. This work includes the considerations of different list structures to store the original problem data and the basis and the testing of various procedures to select the leaving basic variable. This study also examines the sensitivity of the implementation to changes in problem parameters. The results show that the algorithm which is presented here is superior to earlier dual implementations.     

Monitoring real-time CBE growth of GaAs and AlGaAs using dynamic optical reflectivity

Dynamic optical reflectivity (DOR) uses the interference oscillations arising from the multiple reflections, of a normally incident CW laser beam, between the surface of a growing film and the film-substrate interface. The oscillations have a period determined by the refractive index of the film and the laser wavelength. DOR measurements have been made, in real time, during the CBE growth of Al_xGa_1−xAs layers on a GaAs(100) substrate. The results show that the growth rate and the aluminum composition x can be monitored.     

On embeddings of full amalgamated free product C-algebras

We examine the question of when the -homomorphism of full amalgamated free product C-algebras, arising from compatible inclusions of C-algebras , and , is an embedding. Results giving sufficient conditions for to be injective, as well as classes of examples where fails to be injective, are obtained. As an application, we give necessary and sufficient conditions for the full amalgamated free product of finite-dimensional C-algebras to be residually finite dimensional.

     

Precision measurement of the neutron spin asymmetryA(n)(1) and spin-flavor decomposition in the valence quark region

We have measured the neutron spin asymmetry A(n)(1) with high precision at three kinematics in the deep inelastic region at x=0.33, 0.47, and 0.60, and Q(2)=2.7, 3.5, and 4.8 (GeV/c)(2), respectively. Our results unambiguously show, for the first time, that A(n)(1) crosses zero around x=0.47 and becomes significantly positive at x=0.60. Combined with the world proton data, polarized quark distributions were extracted. Our results, in general, agree with relativistic constituent quark models and with perturbative quantum chromodynamics (PQCD) analyses based on the earlier data. However they deviate from PQCD predictions based on hadron helicity conservation.     

LB films of rodlike phthalocyanine aggregates: specular X-ray reflectivity studies of the effect of interface modification on coherence and microstructure

We present here X-ray specular reflectivity (XRR) characterization of the ordering of Langmuir-Blodgett films of the liquid crystalline phthalocyanine (Pc) 2,3,9,10,16,17,23,34-octakis(2-benzyloxyethoxy)copper(II) phthalocyanine, 1, on Si(100) wafers with a native oxide layer and these same substrates modified with monolayers of varying percentages of methyl- and phenyl-terminated silanes. The central copper atom in these Pc's provides for high contrast in X-ray reflectivity for single-bilayer films of 1. The XRR data are modeled as arising from multiple layers of organic material, above and below the rows of copper atoms in the aligned Pc cores; variations in the total thickness of these films, and the spacing between the rows of copper atoms, are attributed to changes in the interaction with the substrate, and changes in the Pc orientation and side chain packing. The most pronounced effect on these parameters comes from variations in the ratio of the phenyl-silane versus methyl-silane content of the substrate modifiers and annealing of these films past their crystalline (K) --> liquid crystalline (LC) mesophase transition temperature. Transfer of multiple bilayers of this Pc leads to additional changes in the thickness of each layer, eventually forming a hexagonal close-packed array, reminiscent of bulk fibers of this material, as revealed by X-ray diffraction (XRD).