Continuous-wave broadly tunable Cr2+:ZnSe laser

We report room-temperature operation of an all-solid-state broadly tunable continuous-wave Cr(2+):ZnSe laser. Output power of 250 mW, an absorbed power slope efficiency of 63%, and continuous tunability from 2138 to 2760 nm are demonstrated.     

Ionization of carbon acids in liquid ammonia

The acidities of various carbon acids in liquid ammonia (LNH(3)) at room temperature were determined by NMR and rates of D-exchange. There is a reasonable linear correlation of the pK(a)s in LNH(3) with those in water and DMSO of slope 0.7 and 0.8, respectively. Carbon acids with an aqueous pK(a) of less than 12 are fully ionized in liquid ammonia. Nucleophilic substitution of benzyl chloride by carbanions in liquid ammonia generates a Br?nsted β(nuc) = 0.38.     

Large Eddy Simulation of a Controlled Diffusion Compressor Cascade

In this research a Controlled Diffusion (CD) compressor cascade stator blade is simulated at a Reynolds number of ??700,000, based on inflow velocity and chord length, using Large Eddy Simulation (LES). A wide range of flow inlet angles are computed, including conditions near the design angle, and at high negative and positive incidence. At all inlet angles the surface pressure distributions are well-predicted by the LES. Near the design angle the computed suction side boundary layer thickness agrees well with experimental data, whilst the pressure side boundary layer is poorly predicted due to the inability of LES to capture natural boundary layer transition on the present grid. A good estimation of the loss is computed near the design angle, whilst at both high positive and negative incidences the loss is less well predicted owing to discrepancies between the computed and experimental boundary layer thickness. At incidences above the design angle a laminar separation bubble forms near the leading edge of the suction surface, which undergoes a transition to turbulence. Similar behaviour is noted on the pressure surface at negative incidence. At high negative incidence contra-rotating vortex pairs are found to form around the leading edge in response to an unsteady stagnation line across the span of the blade. Such structures are not apparent in time-averaged statistical data due to their highly-transient nature.     

The kinetics and mechanisms of aromatic nucleophilic substitution reactions in liquid ammonia

The rates of aromatic nucleophilic substitution reactions in liquid ammonia are much faster than those in protic solvents indicating that liquid ammonia behaves like a typical dipolar aprotic solvent in its solvent effects on organic reactions. Nitrofluorobenzenes (NFBs) readily undergo solvolysis in liquid ammonia and 2-nitrofluorobenzene is about 30 times more reactive than the 4-substituted isomer. Oxygen nucleophiles, such as alkoxide and phenoxide ions, readily displace fluorine of 4-NFB in liquid ammonia to give the corresponding substitution product with little or no competing solvolysis product. Using the pK(a) of the substituted phenols in liquid ammonia, the Br?nsted β(nuc) for the reaction of 4-NFB with para-substituted phenoxides is 0.91, indicative of the removal of most of the negative charge on the oxygen anion and complete bond formation in the transition state and therefore suggests that the decomposition of the Meisenheimer σ-intermediate is rate limiting. The aminolysis of 4-NFB occurs without general base catalysis by the amine and the second-order rate constants generate a Br?nsted β(nuc) of 0.36 using either the pK(a) of aminium ion in acetonitrile or in water, which is also interpreted in terms of rate limiting breakdown of the Meisenheimer σ-intermediate. Nitrobenzene and diazene are formed as unusual products from the reaction between sodium azide and 4-NFB, which may be due to the initially formed 4-nitroazidobenzene decomposing to give a nitrene intermediate, which may then give diazene or be trapped by ammonia to give the unstable hydrazine which then yields nitrobenzene.     

Resting and active states of the ERK2:HePTP complex

The MAP kinase ERK2 (ERK2, extracellular signal-regulated kinase 2) is regulated by numerous phosphatases that tightly control its activity. For example, the hematopoietic tyrosine phosphatase (HePTP) negatively regulates T cell activation in lymphocytes via ERK2 dephosphorylation. However, only very limited structural information is available for these biologically important complexes. Here, we use small-angle X-ray scattering combined with EROS ensemble refinement to characterize the structures of the resting and active states of ERK2:HePTP complexes. Our data show that the resting state ERK2:HePTP complex adopts a highly extended, dynamic conformation that becomes compact and ordered in the active state complex. This work experimentally demonstrates that these complexes undergo significant dynamic structural changes in solution and provides the first structural insight into an active state MAPK complex.     

Improving Liquid Chromatography-Mass Spectrometry Sensitivity Using a Subambient Pressure Ionization with Nanoelectrospray (SPIN) Interface

In this work, the subambient pressure ionization with nanoelectrospray (SPIN) ion source and interface, which operates at ~15–30 Torr, is demonstrated to be compatible with gradient reversed-phase liquid chromatography-MS applications, exemplified here with the analysis of complex samples (a protein tryptic digest and a whole cell lysate). A low liquid chromatographic flow rate (100–400 nL/min) allowed stable electrospray to be established while avoiding electrical breakdown. Efforts to increase the operating pressure of the SPIN source relative to previously reported designs prevented solvent freezing and enhanced charged cluster/droplet desolvation. A 5- to 12-fold improvement in sensitivity relative to a conventional atmospheric pressure nanoelectrospray ionization (ESI) source was obtained for detected peptides.     

Mechanically robust hydrophobized double network hydrogels and their fundamental salt transport properties

Water swollen polymer networks are attractive for applications ranging from tissue regeneration to water purification. For water purification, charged polymers provide excellent ion separation properties. However, many ion exchange membranes (IEMs) are brittle, necessitating the use of thick support materials that ultimately decrease throughput. To this end, novel double network hydrogels (DNHs) with variable water content are prepared and characterized in terms of mechanical and ion transport properties to evaluate their potential utility as tough membrane materials. The first network contains fixed anionic charges, while the other is comprised of a copolymer with varied ratios of hydrophobic ethyl acrylate (EA) and hydrophilic dimethyl acrylamide (DMA) repeat units. Characterization of freestanding DNH films reveals a reduction in water content from 88 to 53 wt% and a simultaneous increase in ultimate stress and strain by ~3.5× and ~4.5×, respectively, for 95%/5% EA/DMA, relative to 100% DMA. Fundamental salt transport properties relevant to water purification, including permeability, solubility, and diffusivity, are measured and systematically compared with conventional membrane materials to inform the development of DNHs for membrane applications. The ability to simultaneously reduce water content and increase mechanical integrity highlights the potential of DNHs as a synthetic platform for future membrane applications.     

Ueber die Bestimmung des Cadmiums

Ohne Zusammenfassung     

Thermoregulatoren

Ohne Zusammenfassung