Synthesis and Study of Olefin Metathesis Catalysts Supported by Redox-Switchable Diaminocarbene 3 Ferrocenophanes

A redox-switchable ligand, N,N'-dimethyldiaminocarbene[3]ferrocenophane (5), was synthesized and incorporated into a series of Ir- and Ru-based complexes. Electrochemical and spectroscopic analyses of (5) Ir(CO)(2)Cl (15) revealed that 5 displayed a Tolman electronic parameter value of 2050 cm(-1) in the neutral state and 2061 cm(-1) upon oxidation. Moreover, inspection of X-ray crystallography data recorded for (5) Ir(cis,cis-1,5-cyclooctadiene)Cl (13) revealed that 5 was sterically less bulky (%V-Bur = 28.4) than other known diaminocarbene[3]ferrocenophanes, which facilitated the synthesis of (5)(PPh3)Cl2Ru-(3-phenylindenylid-1-ene) (18). Complex 18 exhibited quasi-reversible electrochemical processes at 0.79 and 0.98 V relative to SCE, which were assigned to the Fe and Ru centers in the complex, respectively, based on UV-vis and electron pair resonance spectroscopic measurements. Adding 2,3-dichloro-5,6-dicyanoquinone over the course of a ring-opening metathesis polymerization of cis, cis-1,5-cyclooctadiene catalyzed by 18 ([monomer](0)/[18](0) = 2500) reduced the corresponding rate constant of the reaction by over an order of magnitude (pre-oxidation: k(obs) = 0.045 s(-1); post-oxidation: k(obs) = 0.0012 s(-1)). Subsequent reduction of the oxidized species using decamethylferrocene restored catalytic activity (post-reduction: k(obs) = up to 0.016 s(-1), depending on when the reductant was added). The difference in the polymerization rates was attributed to the relative donating ability of the redox-active ligand (i.e., strongly donating 5 versus weakly donating 5(+)) which ultimately governed the activity displayed by the corresponding catalyst.U. S. Army Research Office W911NF-09-1-0446Chemistr

ORFEUS II and IUE Spectroscopy of EX Hydrae

Using ORFEUS-SPAS II FUV spectra, IUE UV spectra, and archival EUVE deep survey photometry, we present a detailed picture of the behavior of the magnetic cataclysmic variable EX Hydrae. Like HUT spectra of this source, the FUV and UV spectra reveal broad emission lines of He II, C II-IV, N III and V, O VI, Si III-IV, and Al III superposed on a continuum which is blue in the UV and nearly flat in the FUV. Like ORFEUS spectra of AM Her, the O VI doublet is resolved into broad and narrow emission components. Consistent with its behavior in the optical, the FUV and UV continuum flux densities, the FUV and UV broad emission line fluxes, and the radial velocity of the O VI broad emission component all vary on the spin phase of the white dwarf, with the maximum of the FUV and UV continuum and broad emission line flux light curves coincident with maximum blueshift of the broad O VI emission component. On the binary phase, the broad dip in the EUV light curve is accompanied by strong eclipses of the UV emission lines and by variations in both the flux and radial velocity of the O VI narrow emission component. The available data are consistent with the accretion funnel being the source of the FUV and UV continuum and the O VI broad emission component, and the white dwarf being the source of the O VI narrow emission component.Comment: 21 pages, 10 Postscript figures; LaTeX format, uses aaspp4.sty; table2.tex included separately because it must be printed sideways - see instructions in the file; accepted on 1999 Feb 20 for publication in The Astrophysical Journa

A Quantitative Non-radial Oscillation Model for the Subpulses in PSR B0943+10

In this paper, we analyze time series measurements of PSR B0943+10 and fit them with a non-radial oscillation model. The model we apply was first developed for total intensity measurements in an earlier paper, and expanded to encompass linear polarization in a companion paper to this one. We use PSR B0943+10 for the initial tests of our model because it has a simple geometry, it has been exhaustively studied in the literature, and its behavior is well-documented. As prelude to quantitative fitting, we have reanalyzed previously published archival data of PSR B0943+10 and uncovered subtle but significant behavior that is difficult to explain in the framework of the drifting spark model. Our fits of a non-radial oscillation model are able to successfully reproduce the observed behavior in this pulsar.Comment: 45 pages, 16 figures, accepted Ap

Uncivil behaviour in the workplace causes mental fatigue and is contagious

Employees on the receiving end tend to ‘pay forward’ the incivility to others, write Christopher C. Rosen, Joel Koopman, Allison S. Gabriel and Russell E. Johnso

A new family of AdS4AdS_4 S-folds in type IIB string theory

We construct infinite new classes of $AdS_4\times S^1\times S^5$ solutions of type IIB string theory which have non-trivial $SL(2,\mathbb{Z})$ monodromy along the $S^1$ direction. The solutions are supersymmetric and holographically dual, generically, to $\mathcal{N}=1$ SCFTs in $d=3$. The solutions are first constructed as $AdS_4\times \mathbb{R}$ solutions in $D=5$ $SO(6)$ gauged supergravity and then uplifted to $D=10$. The solutions all arise as limiting cases of Janus solutions of $d=4$, $\mathcal{N}=4$ SYM theory which are supported both by a different value of the coupling constant on either side of the interface, as well as by fermion and boson mass deformations. As special cases, the construction recovers three known S-fold constructions, which preserve $\mathcal{N}=1,2$ and 4 supersymmetry, as well as a recently constructed $\mathcal{N}=1$ $AdS_4\times S^1\times S^5$ solution (not S-folded). We also present some novel "one-sided Janus" solutions that are non-singular.Comment: 54 pages, 13 figure

Liat1, an arginyltransferase-binding protein whose evolution among primates involved changes in the numbers of its 10-residue repeats

The arginyltransferase Ate1 is a component of the N-end rule pathway, which recognizes proteins containing N-terminal degradation signals called N-degrons, polyubiquitylates these proteins, and thereby causes their degradation by the proteasome. At least six isoforms of mouse Ate1 are produced through alternative splicing of Ate1 pre-mRNA. We identified a previously uncharacterized mouse protein, termed Liat1 (ligand of Ate1), that interacts with Ate1 but does not appear to be its arginylation substrate. Liat1 has a higher affinity for the isoforms Ate1^(1A7A) and Ate1^(1B7A). Liat1 stimulated the in vitro N-terminal arginylation of a model substrate by Ate1. All examined vertebrate and some invertebrate genomes encode proteins sequelogous (similar in sequence) to mouse Liat1. Sequelogs of Liat1 share a highly conserved ∼30-residue region that is shown here to be required for the binding of Liat1 to Ate1. We also identified non-Ate1 proteins that interact with Liat1. In contrast to Liat1 genes of nonprimate mammals, Liat1 genes of primates are subtelomeric, a location that tends to confer evolutionary instability on a gene. Remarkably, Liat1 proteins of some primates, from macaques to humans, contain tandem repeats of a 10-residue sequence, whereas Liat1 proteins of other mammals contain a single copy of this motif. Quantities of these repeats are, in general, different in Liat1 of different primates. For example, there are 1, 4, 13, 13, 17, and 17 repeats in the gibbon, gorilla, orangutan, bonobo, neanderthal, and human Liat1, respectively, suggesting that repeat number changes in this previously uncharacterized protein may contribute to evolution of primates

An Improved Methodology for Multidimensional High- Throughput Preformulation Characterization of Protein Conformational Stability

The Empirical Phase Diagram (EPD) technique is a vector-based multidimensional analysis method for summarizing large data sets from a variety of biophysical techniques. It can be used to provide comprehensive preformulation characterization of a macromolecule’s higher-order structural integrity and conformational stability. In its most common mode, it represents a type of stimulus-response diagram using environmental variables such as temperature, pH, and ionic strength as the stimulus, with alterations in macromolecular structure being the response. Until now EPD analysis has not been available in a high throughput mode because of the large number of experimental techniques and environmental stressor/stabilizer variables typically employed. A new instrument has been developed that combines circular dichroism, UV-absorbance, fluorescence spectroscopy and light scattering in a single unit with a 6-position temperature controlled cuvette turret. Using this multifunctional instrument and a new software system we have generated EPDs for four model proteins. Results confirm the reproducibility of the apparent phase boundaries and protein behavior within the boundaries. This new approach permits two EPDs to be generated per day using only 0.5 mg of protein per EPD. Thus, the new methodology generates reproducible EPDs in high-throughput mode, and represents the next step in making such determinations more routine