Dual-opposite-injection CZE: theoretical aspects and application to organic and pharmaceutical compounds

Several important figures of merit (migration time, efficiency, resolution, resolution per unit time, and electrophoretic selectivity) are quantitatively compared for the first time for conventional CZE and dual-opposite-injection CZE (DOI-CZE). Aspects of DOI-CZE relevant to the separation of organic and pharmaceutical ions (MW>120 Da) are also discussed. Two new approaches to resolve the codetection of anions and cations, hydrodynamic flow-modified DOI-CZE and polarity reversal in combination with asymmetric detector window positioning, are compared with the method of preliminary transport, a variable procedure within sequential sample introduction, using a six-component sample of organic and pharmaceutical compounds. The advantages of DOI-CZE for the simultaneous analysis of organic/pharmaceutical anions and cations are illustrated in a direct comparison of conventional CZE and DOI-CZE for the separation of a ten-component mixture of pharmaceutical ions (five ionized acids and five ionized bases).     

Review of aqueous chiral electrokinetic chromatography (EKC) with an emphasis on chiral microemulsion EKC

The separation of enantiomers using electrokinetic chromatography (EKC) with chiral microemulsions is comprehensively reviewed through December 1, 2006. Aqueous chiral EKC separations based on other pseudostationary phases such as micelles and vesicles or on other chiral selectors such as CDs, crown ethers, glycopeptides, ligand exchange moeities are also reviewed from both mechanistic and applications perspective for the period of January 2005 to December 1, 2006.     

Comparative reactivity of TpRu(L)(NCMe)Ph (L = CO or PMe3): impact of ancillary ligand l on activation of carbon-hydrogen bonds including catalytic hydroarylation and hydrovinylation/oligomerization of ethylene

Complexes of the type TpRu(L)(NCMe)R [L = CO or PMe3; R = Ph or Me; Tp = hydridotris(pyrazolyl)borate] initiate C-H activation of benzene. Kinetic studies, isotopic labeling, and other experimental evidence suggest that the mechanism of benzene C-H activation involves reversible dissociation of acetonitrile, reversible benzene coordination, and rate-determining C-H activation of coordinated benzene. TpRu(PMe3)(NCMe)Ph initiates C-D activation of C6D6 at rates that are approximately 2-3 times more rapid than that for TpRu(CO)(NCMe)Ph (depending on substrate concentration); however, the catalytic hydrophenylation of ethylene using TpRu(PMe3)(NCMe)Ph is substantially less efficient than catalysis with TpRu(CO)(NCMe)Ph. For TpRu(PMe3)(NCMe)Ph, C-H activation of ethylene, to ultimately produce TpRu(PMe3)(eta3-C4H7), is found to kinetically compete with catalytic ethylene hydrophenylation. In THF solutions containing ethylene, TpRu(PMe3)(NCMe)Ph and TpRu(CO)(NCMe)Ph separately convert to TpRu(L)(eta3-C4H7) (L = PMe3 or CO, respectively) via initial Ru-mediated ethylene C-H activation. Heating mesitylene solutions of TpRu(L)(eta3-C4H7) under ethylene pressure results in the catalytic production of butenes (i.e., ethylene hydrovinylation) and hexenes.     

Ternary fluoro-containing polyimide blends and fluoro-containing polyimide/polyester blends

Two ternary miscible fluoro-polyimide blends have been identified. They are 6FDA-3,3′-6F-diamine/6FDA-4,4′- F - diamine/BTDA - 4,4′ - 6FDA blend and 6FDA - 3,3′ - 6F - diamine/6FDA - 4,4′ - 6F - diamine/ODPA - PMDA - 4,4′-6F-diamine blend (6FDA is 2,2′-bis(3,4′-dicarboxy- phenyl)hexafluoro propane dianhydride, 6F-diamine is 2,2′-bis(3-aminophenyl) hexafluoro propane). Their miscibility probably arises from the fact that their diamine parts have hexafluoro isopropylidene groups, their dianhydride parts have similar bond angle, space, rigidity and length. Several 6FDA-polyimides and PCTG 5445 (glycol-modified polycyclohexanedimethanolterephthalate) form- ing miscible blends have also been discovered. These surprising results suggest that hexafluoro-isopropylidene-group containing polyimides are quite intermolecular active and the 1,4-cyclohexane dimethanol component in PCTG 5445 may also offer unique miscibility capability. © 1997 John Wiley & Sons, Ltd.     

Nonlinear Parameter Identification of a Mechanical Interface Based on Primary Wave Scattering

We study stress-wave propagation in an impulsively forced split Hopkinson bar system incorporating a threaded interface. We first consider only primary transmission and reflection and reduce the problem to a first-order, strongly nonlinear ordinary differential equation governing the displacement across the interface, called the primary-pulse model. The interface is modeled as an adjusted-Iwan element, which is characterized by matching experimental and numerical eigenfrequencies as well as primary pulse amplitudes. We find that the adjusted-Iwan element parameters are dependent on preload and impact velocity (input force). A high-order finite element model paired with the identified adjusted-Iwan element is used to simulate multiple transmissions and reflections across the interface. We find that the finite element simulation reproduces the experimental results in both the wavelet and Fourier domains, validating the identification method. Our findings demonstrate that the primary-pulse model can be used for experimental parameter identification of nonlinear interfaces in waveguides.     

Dependence of flame propagation on pressure and pressurizing gas for an Al/CuO nanoscale thermite

The pressure dependence of flame propagation in an Al/CuO nanoscale thermite was studied. Experiments were performed by loosely packing the Al/CuO mixture in an instrumented burn tube, which was placed in a large volume, constant pressure chamber with optical windows. A high-speed camera was used to take photographic data, and six pressure transducers equally spaced along the length of the burn tube were used to measure the local transient pressure. Ambient pressures were varied between 0 and 15 MPa, and three different pressurizing gases were used: argon, helium, and nitrogen. Three modes of propagation were observed. The pressure at which the mode of propagation changed was similar for argon and nitrogen, however, when pressurized with helium, transition occurred at lower pressures. In the low-pressure regime (0–2 MPa) a constant velocity mode with speeds on the order of 1000 m/s was observed. In this region, a convective mode of propagation was dominant. An accelerating regime was observed for a pressure range of approximately 2–5 MPa in argon and nitrogen, with speeds ranging from 100 to 800 m/s. In helium, however, if an accelerating region existed it occurred over a narrow pressure range which was not observed in the present experiments. An oscillating regime was observed in all three gases, in a pressure range of 5–9 MPa for argon and nitrogen, and a range of 2–4 MPa for helium. Velocities in this region are bimodal, and differ by orders of magnitude, suggesting that the propagation mechanism was oscillating between convective and conductive. At relatively high ambient pressures, a constant velocity mode with speeds on the order of 1 m/s was observed for all three gases. The conductive mode of propagation was likely dominant in this region.     

Bridgework ahead! Innovation ecosystems vis-à-vis responsible innovation

Public funding agencies largely support academic research as an effort to stimulate future product commercialization and foster broader societal benefits. Yet, translating research nurtured in academic settings into such outcomes is complex and demands functional interactions between government, academic, and industry, i.e., “triple helix,” organizations within an innovation ecosystem. This article argues that in the spirit of responsible innovation, research funding should build bridges that extend beyond the triple helix stakeholders to connect to peripheral organizations. To support that argument, evidence from agent network analysis gathered from two case studies reveals strong and weak connections, as well as gaps within innovation ecosystems in Switzerland and metropolitan Phoenix, USA. This article offers insights on how innovation ecosystems are aligned or misaligned with responsible innovation.     

A one-bead, one-stock solution approach to chemical genetics: part 1

BACKGROUND: In chemical genetics, small molecules instead of genetic mutations are used to modulate the functions of proteins rapidly and conditionally, thereby allowing many biological processes to be explored. This approach requires the identification of compounds that regulate pathways and bind to proteins with high specificity. Structurally complex and diverse small molecules can be prepared using diversity-oriented synthesis, and the split-pool strategy allows their spatial segregation on individual polymer beads, but typically in quantities that limit their usefulness. RESULTS: We report full details of the first phase of our platform development, including the synthesis of a high-capacity solid-phase bead/linker system, the development of a reliable library encoding strategy, and the design of compound decoding methods both from macrobeads and stock solutions. This phase was validated by the analysis of an enantioselective, diversity-oriented synthesis resulting in an encoded 4320-member library of structurally complex dihydropyrancarboxamides. CONCLUSIONS: An efficient and accessible approach to split-pool, diversity-oriented synthesis using high-capacity macrobeads as individual microreactors has been developed. Each macrobead contains sufficient compound to generate a stock solution amenable to many biological assays, and reliable library encoding allows for rapid compound structure elucidation post-synthesis. This 'one-bead, one-stock solution' strategy is a central element of a technology platform aimed at advancing chemical genetics.     

An efficient synthesis of indane-derived bis(oxazoline) and its application to hetero Diels-Alder reactions on polymer support

Indane-derived bis(oxazolines) were synthesized in two steps and 93% overall yield starting from commercially available substrates. This ligand is as effective as tert-butyl bis(oxazoline) in hetero Diels-Alder reaction both in solution and on polymer support.     

Evidence for kinetic and oxidative stabilization of Rh on Mo-promoted Rh/Al2O3

Carbon monoxide hydrogenation studies on silica- and alumina-supported Rh catalysts conducted in our laboratories as well as those reported in the literature suggest that the addition of early transition-metal oxides to the catalyst surface exerts a promotional influence on active Rh centers. This promotion leads to enhanced oxygenate selectivity. Explanations of the promotional influence of the early transition-metal oxides fall into three categories: (i) kinetic stabilization of small Rh aggregates, (ii) wetting and spreading of the transition-metal oxide, leading to decoration of the surface of Rh crystallites, and (iii) oxidative stabilization of Rh aggregates, altering Rh interactions with sub-carbonyls during reaction. Characterization of the Rh---Mo/γ-Al₂O₃ system provides supporting evidence for both kinetic stabilization and oxidative stabilization of Rh aggregates and suggests that these processes contribute to the enhanced oxygenate selectivity of these materials. Hydrogen and carbon monoxide chemisorption results provide evidence for highly dispersed and oxidatively stabilized Rh aggregates. Even after extended on-stream testing (> 10 h), where metal aggregation is unavoidable, high-resolution transmission electron microscopy, associated energy dispersive spectroscopy, and the use of fast-Fourier transform post-processing to produce optical diffractograms highlight differences in the metal-aggregate morphology.