Catalytic 1,4‐Rhodium(III) Migration Enables 1,3‐Enynes to Function as One‐Carbon Oxidative Annulation Partners in CH Functionalizations

1,3‐Enynes containing allylic hydrogens cis to the alkyne are shown to act as one‐carbon partners, rather than two‐carbon partners, in various rhodium‐catalyzed oxidative annulations. The mechanism of these unexpected transformations is proposed to occur through double C? H activation, involving a hitherto rare example of the 1,4‐migration of a Rh^III species. This phenomenon is general across a variety of substrates, and provides a diverse range of heterocyclic products.     

2D Oligosilyl Metal–Organic Frameworks as Multi‐state Switchable Materials

We report the synthesis of a set of 2D metal–organic frameworks (MOFs) constructed with organosilicon‐based linkers. These oligosilyl MOFs feature linear Si_nMe_2n(C₆H₄CO₂H)₂ ligands (lin‐Si_n, n=2, 4) connected by Cu paddlewheels. The stacking arrangement of the 2D sheets is dictated by van der Waals interactions and is tunable by solvent exchange, leading to reversible structural transformations between many crystalline and amorphous phases.     

An integrated microfluidic device for influenza and other genetic analyses

An integrated microfluidic device capable of performing a variety of genetic assays has been developed as a step towards building systems for widespread dissemination. The device integrates fluidic and thermal components such as heaters, temperature sensors, and addressable valves to control two nanoliter reactors in series followed by an electrophoretic separation. This combination of components is suitable for a variety of genetic analyses. As an example, we have successfully identified sequence-specific hemagglutinin A subtype for the A/LA/1/87 strain of influenza virus. The device uses a compact design and mass production technologies, making it an attractive platform for a variety of widely disseminated applications.     

Some people and places important in the history of analytical chemistry in Italy

The people and places of importance to the history of chemistry in Italy have been reviewed with particular reference to Analytical Chemistry. Correspondence: D. Thorburn Burns, The Science Library, The Queen’s University of Belfast, Belfast BT9 5EQ, Northern Ireland     

Nanoscale Science and Technology at Los Alamos National Laboratory

Research in the emerging field of nanoscale science and technology has grown steadily at Los Alamos National Laboratory since 1990. This article summarizes some of this work, examining research highlights within the seven key categories of nanoscience in which Los Alamos has ongoing projects, capabilities, and facilities: (1) Materials and chemistry, (2) Theory and modeling, (3) Bioscience, (4) Investigative tools and facilities, (5) Sensors and devices, (6) Synthesis and fabrication, and (7) Education and outreach. Future research horizons are indicated throughout while institutional strategies for advancing nanoscale science are summarized at the end.     

The extraction, determination and speciation of tributyltin in seawater

Summary Methods have been developed for the determination, by carbon-furnace atomisation atomic absorption spectrophotometry, of inorganic and of total butyltin in seawater. Concentration/separations are based on the solvent extraction of organotin species directly into toluene and of inorganic tin as its tin(IV) 8-hydroxyquinoline chelate into chloroform. Detection limits are 0.7–0.8 ng.

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Extraktion, Bestimmung und Speziation von Tributylzinn in Seewasser

     

Compatibility studies of blends of polycarbonate and poly(ethylene terephthalate)

Blends of bisphenol-A polyarbonate (PC) and poly(ethylene terephthalate) (PET) has been investigated by differential scanning calorimetry and scanning electron microscopy. Blends were prepared by screw extrusion and solution casting with weight fractions of PC in the blends varying from 0.90 to 0.10. From the measured glass transition temperature (T_g) and apparent weight fractions of PC and PET dissolved in each phase, it appears that PET dissolves more in the PC-rich phase than does the PC in the PET-rich phase. The composition-dependent values of the Flory–Huggins polymer–polymer–interaction parameter were determined and found to be from 0.054 to 0.037 for extruded blends at 275°C and from 0.058 to 0.040 for solution casting at 25°C. The interaction parameter decreases with increasing PET concentration. This result is consistent with the values of the T_gs, the microscopy study, and the measured extrudate swell ratios which show that compatibility increases more in the PET-rich compositions than in the PC-rich compositions. The PC–PET blends are not microscopically miscible for all the blend compositions.     

The existence of disjoint smallest ideals in the two natural products on β S

No abstract. September 13, 1999     

The complexity of a basic impact mapping for rigid bodies with impacts and friction

We consider two impact mappings, the Brach impact mapping and an energetic impact mapping, for rigid-body mechanisms with impacts and friction. The two impact mappings represent the opposite end of the spectrum from basic to advanced impact mappings. Both impact mappings are briefly derived and described. For the Brach impact mapping we will introduce the concept of impulse ratio and discuss how the kinetic energy changes during an impact as the impulse ratio is varied. This analysis is used to further extend the Brach impact mapping to cover situations that were previously omitted. Finally, we make comparisons between the two impact mappings and show how the Painlevé paradox appears in the two impact mappings. The conclusion of the comparisons is that while the basic impact mapping seems easy to implement in a computer simulator it may in the end be more complex and also introduce unnecessary complications that are completely artificial.     

Kr-PLIF for scalar imaging in supersonic flows

Experiments were performed to explore the use of two-photon planar laser-induced fluorescence (PLIF) of krypton gas for applications of scalar imaging in supersonic flows. Experiments were performed in an underexpanded jet of krypton, which exhibited a wide range of conditions, from subsonic to hypersonic. Excellent signal-to-noise ratios were obtained, showing the technique is suitable for single-shot imaging. The data were used to infer the distribution of gas density and temperature by correcting the fluorescence signal for quenching effects and using isentropic relations. The centerline variation of the density and temperature from the experiments agree very well with those predicted with an empirical correlation and a CFD simulation (FLUENT). Overall, the high signal levels and quantifiable measurements indicate that Kr-PLIF could be an effective scalar marker for use in supersonic and hypersonic flow applications.