Laboratory simulation of atmospheric turbulence-induced optical wavefront distortion

Real-time liquid crystal television-based technique for simulating optical wavefront distortion due to atmospheric turbulence is presented and demonstrated. A liquid crystal television (LCTV) operating in the “phase mostly” mode was used as an array of spatially correlated phase delays. A movie of the arrays in motion was then generated and displayed on the LCTV. The turbulence simulation system was verified by passing a collimated and doubled diode pumped Nd:YVO₄ laser beam (532 nm) through the transparent LCTV screen. The beam was then passed through a lens and the power spectra of the turbulence information carrying beam was detected as a measure of the far-field distribution. The same collimated laser beam, without the LCTV, was also transmitted down an open-air range and the power spectra detected as a measure of a real far-field distribution. Accepted turbulence parameters were measured for both arrangements and then compared.     

Multi-iron wells-Dawson heteropolytungstates. Electrochemical probing of siderophoric behavior in sandwich-type complexes

The demetalation process of 10 multi-iron Wells-Dawson polyoxometalates is studied by cyclic voltammetry and controlled potential coulometry. Eight sandwich-type complexes (alphaalphaalphaalpha-Na(16)[(NaOH(2))(2)(Fe(III))(2)(X(2)W(15)O(56))(2)], alphaalphabetaalpha-Na(14)[(NaOH(2))(Fe(III)OH(2))(Fe(III))(2)(X(2)W(15)O(56))(2)], alphabetabetaalpha-Na(12)[(Fe(III)OH(2))(2)(Fe(III))(2)(X(2)W(15)O(56))(2)], and alphabetabetaalpha-Na(14)[(Mn(II)OH(2))(2)(Fe(III))(2)(X(2)W(15)O(56))(2)] (where X = P(V) or As(V))) and two monomeric complexes (alpha-Na(11)[(P(2)(Fe(III)Cl)(2)(Fe(III)OH(2))W(15)O(59))] and alpha-Na(11)[(As(2)(Fe(III)Cl)(2)Fe(III)OH(2))W(15)O(59))]) were selected for this study. All 10 complexes show Fe(III) waves which are well-separated from the redox activity of the W(VI) centers. At room temperature and under mild conditions, iron release from the complexes is observed upon reduction of the Fe(III) centers. This release is controlled by the ionic strength of the medium, the nature and concentration of the anions present in the supporting electrolyte, and by the pH of the solution. This behavior parallels those described for most siderophores which depend on the same parameters.     

Application of the essential work of fracture concept to nanostructured polymer materials

The first part of the paper deals with a critical discussion of the methodical basis of essential work of fracture (EWF) concept with respect to the specimen geometry (especially the notch depth) and application to polymers. In the second part, an in situ testing device, which combines a tensile testing machine with an optical strain-field measuring system, has successfully demonstrated possibility of characterization of fracture behaviour of polystyrene-polybutadiene block copolymers and block copolymer/homopolymer blends as examples of nanostructured polymer materials. It has been shown that knowledge of the time evolution of the strain field close to the crack tips leads to a simple verification of the basic precondition for the applicability of the EWF concept, the precondition “plastic zone coalescence-before-stable crack propagation”.     

Multiple nitrene insertions into metal-sulfur bonds of dithiocarbamate complexes: synthesis of sulfido-amido and zwitterionic tetraamido complexes

The iodine(III) reagent, PhI[double bond, length as m-dash]NTs, acts as a source of the nitrene fragment NTs, which undergoes facile insertion into the metal-sulfur bonds of a range of dithiocarbamate complexes. Addition of two equivalents of PhI=NTs to [M(S(2)CNR2)2] affords sulfido-amido complexes [M{SC(NR2)SNTs}2](M=Ni, Cu), which insert two further nitrene fragments to afford zwitterionic tetraamido complexes [M{TsNSC(NR2)SNTs}2](M=Co, Ni, Cu). Crystallographic studies have been carried out on both types of complex allowing possible resonance hydrids of the new ligand types to be assessed.     

Stereocontrolled synthesis of cis-dibenzoquinolizine chlorofumarates: curare-like agents of ultrashort duration

The quaternizations of dibenzoquinolizines 9 and 14 with 3-halo-1-propanols are highly cis-selective (94-100% cis), results consistent with the N-methylation of O-methylcapaurine (7b), but in contrast to the proposed trans-stereochemistry of dibenzo[a,h]quinolizine methiodide 10 and the analogous quaternizations of 1-benzyl- and 1-phenylisoquinoline congeners 5b and 5c. In this report, we describe stereoselective preparation of the unique cis-dibenzoquinolizinium propanols 15 and 16and their transformation into bis- and mixed-onium chlorofumarates 19, 20ab, and 26. Dibenzo[a,g]quinolizinium propanol 15 was prepared enantioselectively in three steps from dihydroisoquinoline 11. Asymmetric transfer hydrogenation of 11 in the presence of triethylamine/formic acid and Noyori's chiral ruthenium catalyst 12 produced R-(-)-5',8-dimethoxynorlaudanosine (13) in 98% yield and 87% ee. Pictet-Spengler cyclization of 13 in formalin/formic acid afforded the dibenzo[a,g]quinolizine 14 in 65% yield. Quaternization of 14 with 3-chloro-1-propanol under Finkelstein conditions generated cis-dibenzoquinolizinium propanol 15 in 85% yield with >94% cis-selectivity. The cis-dibenzo[a,h]quinolizinium propanol 16 was obtained as a single stereoisomer by reaction of the known tetramethoxyquinolizine 9 with neat 3-iodo-1-propanol. Bis-onium chlorofumarates 18 and 19 and the mixed-onium derivative 20ab were prepared by a pool synthesis procedure from (1R)-trans-6a, 16, and chlorofumaryl chloride (17). Mixed-onium alpha-chlorofumarate 26 was synthesized from (1S)-trans-6d, 15 and (+/-)-trans-2,3-dichlorosuccinic anhydride (22), employing a recently disclosed chlorofumarate mixed-diester synthesis. The title compounds (19, 20ab, and 26) displayed curare-like effects of ultrashort duration in rhesus monkeys.     

Novel fragmentation pathway for CID of (b<Subscript>n</Subscript>−1+Cat)<Superscript>+</Superscript> ions from model,metal cationized peptides

We report a new fragmentation pathway for the CID of (b3 - 1 + Cat)+ product ions derived from the model peptide AXAG, where X = beta-alanine, gamma-aminobutyric acid, epsilon-amino-n-caproic acid, or 4-aminomethylbenzoic acid. By changing the amino acid to the C-terminal side of the amino acid X, and incorporating 15N and 13C labeled residues at the same position, we conclude that the dissociation pathway most likely leads to a metal cationized nitrile. With respect to the various amino acids at position X, the putative nitrile product becomes more prominent, relative to the conventional (a3 - 1 + Cat)+ species, in the order beta-alanine < gamma-aminobutyric acid < epsilon-aminocaproic acid < 4-aminomethylbenzoic acid. The pathway is not observed for peptides with alpha-amino acids at position X. The product ion is observed most prominently during the CID of Li+ and Na+ cationized peptides, only to a small extent for Ag+ cationized peptides, and not at all from protonated analogues.