Mechanism of H(2) evolution from a photogenerated hydridocobaloxime

Proton transfer from the triplet excited state of brominated naphthol to a difluoroboryl bridged Co(I)-diglyoxime complex, forming Co(III)H, was monitored via transient absorption. The second-order rate constant for Co(III)H formation is in the range (3.5-4.7) × 10(9) M(-1) s(-1), with proton transfer coupled to excited-state deactivation of the photoacid. Co(III)H is subsequently reduced by excess Co(I)-diglyoxime in solution to produce Co(II)H (k(red) = 9.2 × 10(6) M(-1) s(-1)), which is then protonated to yield Co(II)-diglyoxime and H(2).     

Electrochemical and Surface Properties of Multilayer Films Based on a Ru2+ Metallodendrimer and the Mixed Addenda Dawson Heteropolyanion

The successful formation of organized multilayer assemblies, formed from the Dawson type mixed addenda heteropolyanion, [P₂W₁₇ V^IVO₆₂]^8?, and a Ru²⁺ pentaerythritol based metallodendrimer, [RuDen]⁸⁺, has been achieved on carbon electrode surfaces. Cyclic voltammetric studies of the assembly across a wide pH domain, namely, 2 to 7 was possible. Upon redox switching, the redox couples associated with the Ru^III/II redox system, of the cationic metallodendrimer, and both the V^IV/V and the tungsten‐oxo framework of the heteropolyanion, were clearly evident. The multilayer assembly exhibited good stability towards both redox cycling and soaking over extended periods of time in aqueous buffer solutions. In addition, the constructed multilayer films were found to be quite compact in nature. The films were further characterized by X‐ray photoelectron spectroscopy (XPS) to determine their elemental composition. Surface morphology of the multilayer films was determined by atomic force microscopy (AFM). The electrocatalytic reduction of iodate by the multilayer film was also investigated.     

Phenylphosphatrioxa-adamantanes: bulky, robust, electron-poor ligands that give very efficient rhodium(I) hydroformylation catalysts

The cage phosphines 1,3,5,7-tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane (1a) and 1,3,5,7-tetraethyl-6-phenyl-2,4,8,trioxa-6-phosphaadamantane (1b) have been made by the acid catalysed addition of PhPH(2) to the appropriate beta-diketones; the acid used (HCl, H(3)PO(4) or H(2)SO(4)) and its concentration affect the rate and selectivity of these condensation reactions. Phosphines 1a and 1b react with [PdCl(2)(NCPh)(2)] to form complexes trans-[PdCl(2)(1a)(2)](2a) and trans-[PdCl(2)(1b)(2)](2b) as mixtures of rac and meso diastereoisomers. The platinum(II) chemistry is more complicated and when 1a or 1b is added to [PtCl(2)(cod)], equilibrium mixtures of trans-[PtCl(2)L(2)] and [Pt(2)Cl(4)L(2)](L = or ) are formed in CH(2)Cl(2) solution. Meso/rac mixtures of trans-[MCl(CO)(1a)(2)] M = Ir (6a) or Rh (7a) are formed upon treatment of MCl(3).nH(2)O with an excess of 1a and the anionic cobalt complex [NHEt(3)][CoCl(3)(1a)](9) was isolated from the product formed by CoCl(2).6H(2)O and 1a. The nu(CO) values from the IR spectra of 6a and 7a suggest that 1a resembles a phosphonite in its bonding to Rh and Ir. Crystal structures of meso-2a, meso-2b, rac-6a and 9 are reported and in each case a small intracage C-P-C angle of ca. 94 degrees is observed; this may partly explain the bonding characteristics of ligands 1a and 1b. The cone angles for 1a and 1b are similar and large (ca. 200 degrees). Rhodium complexes of ligands 1a and 1b are hydroformylation catalysts with similarly high activity to catalysts derived from phosphites. The catalysts derived from 1a and 1b gave unusually low linear selectivity in the hydroformylation of hexenes. This feature has been further exploited in quaternary-selective hydroformylations of unsaturated esters; catalysts derived from 1a give better yields and regioselectivities than any previously reported catalyst.     

Efficient asymmetric hydrogenation with rhodium complexes of C(1)-symmetric 2,5-dimethylphospholane-diphenylphosphines

The unsymmetrical, optically active ligands 1,2-C(6)H(4)(PPh(2))((R,R)-2,5-dimethylphospholanyl) and the new 1,1'-Fe(C(5)H(4))(2)(PPh(2))((R,R)-2,5-dimethylphospholanyl) form complexes of the type [PtCl(2)(diphos)] and [Rh(diphos)(diene)][BF(4)]. The crystal structure of reveals that only one quadrant is blocked. Asymmetric hydrogenation of acrylic esters and enamides using and as catalysts show that the phenylene-backboned diphosphine gives a more efficient catalyst in terms of asymmetric induction than the more flexible ferrocene-backboned diphosphine. The best results, which were obtained with and enamide substrates, exceeded those obtained with Duphos catalysts. The rate of hydrogenation of the enamides with was 10 times faster than with [Rh(Duphos)(diene)][BF(4)]. A quadrant diagram can be used to predict the configuration of the major product, provided it is assumed to be derived from the less sterically congested intermediate.     

Membrane-permeable and -impermeable sensors of the Zinpyr family and their application to imaging of hippocampal zinc in vivo

Esterification of fluorescent biosensors is a common strategy used to trap probes within the cell. Zinpyr-1 (ZP1) is a fluorescein-based bright fluorescent sensor for divalent zinc that is cell permeable without prior modification. We describe here the synthesis and characterization of ZP1 sensors containing a carboxylic acid or ethyl ester functionality at the 5 or 6 position of the fluorescein. The presence of an electronegative carboxylate decreases the proton-induced background fluorescence of the probe by lowering the pKa of the benzylic amines responsible for fluorescence quenching. The charged species ZP1(6-CO2-) is membrane-impermeant, whereas the permeability of the neutral ZP1(5/6-CO2Et) is similar to that of the parent sensor. Intracranial microinfusion of ZP1(6-CO2Et) into rat hippocampus produces reduced staining of vesicular zinc in neuropil and very clear delineation of zinc-positive injured neuronal somata and dendrites as compared with ZP1.     

Kerr constant of water from 280 to 350 K at 632.8 nm

The Kerr constant (B_T) of deionized liquid water was measured in the temperature range from 280 K to 350 K using 2 μs duration electric pulse fields up to 50 kV cm^?1. The value of B_T has been determined as 2.92 × 10^?14 mV^?2 at 298 K. Results indicate a steady decrease in the value of the Kerr constant with the rise of temperature.     

Micro-patterning of NdFeB and SmCo magnet films for integration into micro-electro-mechanical-systems

The integration of high-performance RE-TM (NdFeB and SmCo) hard magnetic films into micro-electro-mechanical-systems (MEMS) requires their patterning at the micron scale. In this paper we report on the applicability of standard micro-fabrication steps (film deposition onto topographically patterned substrates, wet etching and planarization) to the patterning of 5-8 μm thick RE-TM films. While NdFeB comprehensively fills micron-scaled trenches in patterned substrates, SmCo deposits are characterized by poor filling of the trench corners, which poses a problem for further processing by planarization. The magnetic hysteresis loops of both the NdFeB and SmCo patterned films are comparable to those of non-patterned films prepared under the same deposition/annealing conditions. A micron-scaled multipole magnetic field pattern is directly produced by the unidirectional magnetization of the patterned films. NdFeB and SmCo show similar behavior when wet etched in an amorphous state: etch rates of approximately 1.25 μm/min and vertical side walls which may be attributed to a large lateral over-etch of typically 20 μm. Chemical-mechanical-planarization (CMP) produced material removal rates of 0.5-3 μm/min for amorphous NdFeB. Ar ion etching of such films followed by the deposition of a Ta layer prior to film crystallization prevented degradation in magnetic properties compared to non-patterned films.     

Condensation of wet steam on a horizontal tube with additional droplet deposition

A theory is presented for condensation of downward flowing wet vapour on a horizontal tube. The vapour is assumed to consist of dry saturated vapour and uniformly distributed liquid droplets flowing independently of each other. In addition the droplets are assumed to be so large that they fall vertically on to the tube surface and are unaffected by the vapour flow around the cylinder. The results show that the heat transfer coefficients are extremely dependent on both the droplet mass flux and velocity as well as the steam velocity.     

Affinity purification of secreted alkaline phosphatase produced by baculovirus expression vector system

Human secreted alkaline phosphatase (SEAP) was produced in a stablytransformed Spodoptera frugiperda Sf-9 insect cell line (Sfb4GalT) following infection with a recombinant Autographa californica multiple nuclear polyhedrovirus containing the SEAP gene under control of the polyhedrin promoter. An affinity chromatographic column prepared by linking 4-aminobenzylphosphonic acid to histidyl-expoxy-Sepharose was used to isolate SEAP from the cell supernatant following removal of cells and virus and 10-fold concentration through ultrafiltration. We found that the binding of SEAP on the affinity matrix follows the Langmuir isotherm model. In addition, either recycling SEAP sample through the column for 24 h or loading high SEAP concentrations resulted in a high-purity product. Some nonspecific binding of protein on the matrix occurred when low concentrations of SEAP sample were loaded. Finally, we found that SEAP binding occurs rapidly, i.e., within 30 min of adding the SEAP sample to the affinity matrix.     

Emptying and filling a tunnel bronze

The classical orthorhombic layered phase of V₂O₅ has long been regarded as the thermodynamic sink for binary vanadium oxides and has found great practical utility as a result of its open framework and easily accessible redox states. Herein, we exploit a cation-exchange mechanism to synthesize a new stable tunnel-structured polymorph of V₂O₅ (ζ-V₂O₅) and demonstrate the subsequent ability of this framework to accommodate Li and Mg ions. The facile extraction and insertion of cations and stabilization of the novel tunnel framework is facilitated by the nanometer-sized dimensions of the materials, which leads to accommodation of strain without amorphization. The topotactic approach demonstrated here indicates not just novel intercalation chemistry accessible at nanoscale dimensions but also suggests a facile synthetic route to ternary vanadium oxide bronzes (M_xV₂O₅) exhibiting intriguing physical properties that range from electronic phase transitions to charge ordering and superconductivity.