Electroluminescence in ruthenium(II) complexes

We have investigated the electrochemical, spectroscopic, and electroluminescent properties of a family of diimine complexes of Ru featuring various aliphatic side chains as well as a more extended pi-conjugated system. The performance of solid-state electroluminescent devices fabricated from these complexes using indium tin oxide (ITO) and gold contacts appears to be dominated by ionic space charge effects. Their electroluminescence efficiency was limited by the photoluminescence efficiency of the Ru films and not by charge injection from the contacts. The incorporation of di-tert-butyl side chains on the dipyridyl ligand was found to be the most beneficial substitution in terms of reducing self-quenching of luminescence.     

Phenylpropanoids from Umbilicus pendulinus

Phytochemical investigation of the leaves of Umbilicus pendulinus afforded in addition to 2-O-caffeoyl malate, isoquercitrin and Z-venusol, the new isomer E-venusol. Special NMR experiments were carried out to elucidate the configuration of the two latter compounds.     

Auditorium acoustic modelling now

Acoustic scale modelling of auditoria now has a history extending back half a century. Although progress has been intermittent, the essential viability of the modelling process has guaranteed continued elaboration of testing techniques. Modelling techniques have now achieved a certain sophistication and auditorium models have proved very valuable as consultancy and research aids. The work of Jordan and other groups involved in acoustic modelling of auditoria is reviewed briefly with a discussion of the scale factors used and the nature of testing. The current techniques for both objective and subjective model testing are discussed, concluding in each case with an assessment of the level of contribution each can make to auditorium design.     

Capillary electrophoretic separation of uncharged polymers using polyelectrolyte engines. Theoretical model

Fixed-size moving window evolving factor analysis and base peak chromatograms have been used for peak purity detection in data generated with LC-MS. The two methods were evaluated with both real and simulated data and were found to be fast and complementary to each other. When a possibly impure peak is detected, it is suggested that further information can be obtained from local principal component analysis modelling and comparative mass chromatogram plots.     

Polymeric matrices for DNA sequencing by capillary electrophoresis

We review the wide range of polymeric materials that have been employed for DNA sequencing separations by capillary electrophoresis. Intensive research in the area has converged in showing that highly entangled solutions of hydrophilic, high molar mass polymers are required to achieve high DNA separation efficiency and long read length, system attributes that are particularly important for genomic sequencing. The extent of DNA-polymer interactions, as well as the robustness of the entangled polymer network, greatly influence the performance of a given polymer matrix for DNA separation. Further fundamental research in the field of polymer physics and chemistry is needed to elucidate the specific mechanisms by which DNA is separated in dynamic, uncross-linked polymer networks.     

Privacy and pricing personal information

The issues we address here are – How should a firm (e.g. Internet service provider (ISP)) that is capable of collecting personal information (browsing information, purchase history, etc.) about consumers, price its service, given that consumers vary in their valuation for privacy, and also vary in terms of the value of their personal information to a third party (firms that need consumer information)? Should the firm have a blanket policy of never collecting, or a policy of always collecting and revealing information? Surprisingly we find that in some cases the collector of information may be no worse off in the asymmetric information case than in the full information case. The paper provides a justification for the strategy of some firms such as ISP’s which never collect information and also for the strategy of other firms, like grocery stores that do. We also find that it is non-optimal for the firm to design contracts where the consumer can choose an intermediate level of privacy.     

Particle size control and dependence on solution pH of carboxylate–alumoxane nanoparticles

A series of water dispersible carboxylate–alumoxane nanoparticles were prepared by the reaction of various carboxylic acids with the mineral boehmite. The acids used were: acetic (A–H), methoxyacetic (MA–H), methoxyethoxyacetic (MEA–H), methoxyethoxyethoxyacetic (MEEA–H), and lysine (L–H). For each of the derived carboxylate–alumoxanes, particle size measurements were obtained by means of photon correlation spectroscopy (PCS) as a function of solution pH. In all cases, at higher pHs, slight increases in solution basicity corresponded to large increases in particle size. At lower pHs, however, changes in solution basicity yielded only slight to moderate increases in particle size. It was also found during these investigations that methoxyacetic–alumoxane (MA–A) had a large buffering capacity, and that this effect could be explained by correlation with the aluminum:carboxylate group ratio for the various carboxylate–alumoxanes.     

Synthesis and characterization of aryl substituted bis(2-pyridyl)amines and their copper olefin complexes: investigation of remote steric control over olefin binding

The aryl-functionalized pyridylamine 2-(i)PrC(6)H(4)N(H)py (1) and bis(2-pyridyl)amines of the type ArN(py)(2) for Ar = Mes (2), 2,6-Et(2)C(6)H(3) (3), 2-(i)PrC(6)H(4) (4), 2,6-(i)Pr(2)C(6)H(3) (5), and 1-naph (6), have been prepared by the palladium-catalyzed cross-coupling of substituted anilines with 2-bromopyridine, and have been characterized by (1)H and (13)C NMR NMR, FTIR, MS, and TGA. Complexes of these new N-aryl bis(2-pyridyl)amines have been prepared for the acid salts [H{ArN(py)(2)}]BF(4) where Ar = Mes (7) and 2-(i)PrC(6)H(4) (8), and the dimeric bridged complexes [Cu{ArN(py)(2)}(μ-X)(Y)](2) where X/Y = Cl(-) and Ar = Ph (9), 2-(i)PrC(6)H(4) (10), and 1-naph (11), in addition to X = OH(-), Y = H(2)O and Ar = Mes (12). The olefin complexes [Cu(Ar-dpa)(styrene)]BF(4) for Ar = Ph (13), Mes (14), 2-(i)PrC(6)H(4) (15), and 1-naph (16), in addition to the norborylene complexes of Ar = Mes (17) and 2-(i)PrC(6)H(4) (18) have been prepared and characterized by (1)H and (13)C NMR, FTIR, and TGA. The crystal structures have been determined for compounds 1-17. Secondary amine 1 crystallizes in hydrogen-bonded head-to-tail dimers, while the N-aryl bis(2-pyridyl)amines 2-6 crystallize in a three-bladed propellar conformation, having nearly planar geometries about the amine nitrogen. The geometry about copper centers in the dimeric complexes 9-12 is distorted trigonal bypyramidal, with the axial positions occupied by one of the two pyridyl nitrogens and one of the bridging ligands (i.e., Cl or OH). The copper atoms in each of the olefin complexes 13-17 are coordinated to the two pyridine nitrogen atoms and the appropriate olefin; consistent with a pseudo three-coordinate Cu(I) cation. Distortion of pyridyl ring geometries about the copper centers, and concomitant bending of the aryl groups away from the CuN(amine) vectors were found to correlate with the steric bulk of the aryl group present in both dimeric and olefin complexes. Such distortion is also observed to a lesser extent in the acid salts as well. The (1)H and (13)C NMR spectra of [Cu(Ar-dpa)(olefin)]BF(4) exhibit an upfield shift in the olefin signal as compared to free olefin. A good correlation exists between the (1)H and (13)C NMR Δδ values and olefin dissociation temperatures, confirming that the shift of the olefin NMR resonances upon coordination is associated with the binding strength of the complex.