Examining the Effects of Monomer and Catalyst Structure on the Mechanism of Ruthenium-Catalyzed Ring-Opening Metathesis Polymerization

The mechanism of Ru-catalyzed ring-opening metathesis polymerization (ROMP) is studied in detail using a pair of third generation ruthenium catalysts with varying sterics of the N-heterocyclic carbene (NHC) ligand. Experimental evidence for polymer chelation to the Ru center is presented in support of a monomer-dependent mechanism for polymerization of norbornene monomers using these fast-initiating catalysts. A series of kinetic experiments, including rate measurements for ROMP, rate measurements for initiation, monomer-dependent kinetic isotope effects, and activation parameters were useful for distinguishing chelating and nonchelating monomers and determining the effect of chelation on the polymerization mechanism. The formation of a chelated metallacycle is enforced by both the steric bulk of the NHC and by the geometry of the monomer, leading to a ground-state stabilization that slows the rate of polymerization and also alters the reactivity of the propagating Ru center toward different monomers in copolymerizations. The results presented here add to the body of mechanistic work for olefin metathesis and may inform the continued design of catalysts for ROMP to access new polymer architectures and materials

Screening and isolating eastern redcedar phytochemicals for creating economic opportunities in Missouri [abstract]

Eastern Redcedar (ERC) is one of the most widely distributed tree species in Missouri. The ERC is an important source of bioactive secondary metabolites, but very few of these biologically active compounds have been identified, purified or commercialized. An interdisciplinary collaboration between MU scientists was initiated in 2007 to identify and isolate biologically active phytochemicals from ERC tissues for possible commercial application. Our team has identified and purified biologically active compounds from leaves (needles) and fruit of the ERC. Many of these isolated diterpenoids not only have shown strong anti-microbial activities against a wide range of pathogenic bacteria, but also strong inhibitory activities against melanin biosynthesis. Recently, the isolated tricyclic diterpenoids have been recognized as promising anti-inflammatory, anti-microbial, and skin whitening agents by cosmetic and pharmaceutical industries. The objectives of the proposed study are to: 1) isolate and characterize the biologically active phytochemicals, and 2) elucidate chemical structures of active compounds and their associated mode of actions. The first of these compounds to be characterized is the purified bioactive diterpenoid. The purified bioactive diterpenoid was found to have a significant inhibitory effect on the growth of all Gram positive pathogens tested. This inhibition of Gram positive bacteria is likely due to action on the cell division machinery, for affected cells elongate without proper separation. Additional compounds have activity on fungal agents, as well as potential anti-melanin activities. The knowledge generated from our research will provide the opportunities to turn abundant, low-value, renewable materials from the ERC into a lucrative, high technology industry in Missouri. INVENTOR(S): Chun-Ho Lin; Brian M. Thompson; Hsin-Yeh Hsieh; Robert J. Kremer; Robert N. Lerch; Michael A. Gold and Harold E. Garrett CONTACT INFO: Harriet F. Francis, MS; J.D.; [email protected]; 573.884.0374 Per Stromhaug, Ph.D., MBA; [email protected]; 573.884.355

A threshold phenomenon for embeddings of H0mH^m_0 into Orlicz spaces

We consider a sequence of positive smooth critical points of the Adams-Moser-Trudinger embedding of $H^m_0$ into Orlicz spaces. We study its concentration-compactness behavior and show that if the sequence is not precompact, then the liminf of the $H^m_0$-norms of the functions is greater than or equal to a positive geometric constant.Comment: 14 Page

Localization and chiral symmetry in 2+1 flavor domain wall QCD

We present results for the dependence of the residual mass of domain wall fermions (DWF) on the size of the fifth dimension and its relation to the density and localization properties of low-lying eigenvectors of the corresponding hermitian Wilson Dirac operator relevant to simulations of 2+1 flavor domain wall QCD. Using the DBW2 and Iwasaki gauge actions, we generate ensembles of configurations with a $16^3\times 32$ space-time volume and an extent of 8 in the fifth dimension for the sea quarks. We demonstrate the existence of a regime where the degree of locality, the size of chiral symmetry breaking and the rate of topology change can be acceptable for inverse lattice spacings $a^{-1} \ge 1.6$ GeV.Comment: 59 Pages, 23 figures, 1 MPG linke

Quad-Chip Double-Balanced Frequency Tripler

Solid-state frequency multipliers are used to produce tunable broadband sources at millimeter and submillimeter wavelengths. The maximum power produced by a single chip is limited by the electrical breakdown of the semiconductor and by the thermal management properties of the chip. The solution is to split the drive power to a frequency tripler using waveguides to divide the power among four chips, then recombine the output power from the four chips back into a single waveguide. To achieve this, a waveguide branchline quadrature hybrid coupler splits a 100-GHz input signal into two paths with a 90 relative phase shift. These two paths are split again by a pair of waveguide Y-junctions. The signals from the four outputs of the Y-junctions are tripled in frequency using balanced Schottky diode frequency triplers before being recombined with another pair of Y-junctions. A final waveguide branchline quadrature hybrid coupler completes the combination. Using four chips instead of one enables using four-times higher power input, and produces a nearly four-fold power output as compared to using a single chip. The phase shifts introduced by the quadrature hybrid couplers provide isolation for the input and output waveguides, effectively eliminating standing waves between it and surrounding components. This is accomplished without introducing the high losses and expense of ferrite isolators. A practical use of this technology is to drive local oscillators as was demonstrated around 300 GHz for a heterodyne spectrometer operating in the 2-3-THz band. Heterodyne spectroscopy in this frequency band is especially valuable for astrophysics due to the presence of a very large number of molecular spectral lines. Besides high-resolution radar and spectrographic screening applications, this technology could also be useful for laboratory spectroscopy

Telomere dysfunction accurately predicts clinical outcome in chronic lymphocytic leukaemia, even in patients with early stage disease

© 2014 John Wiley & Sons Ltd. Defining the prognosis of individual cancer sufferers remains a significant clinical challenge. Here we assessed the ability of high-resolution single telomere length analysis (STELA), combined with an experimentally derived definition of telomere dysfunction, to predict the clinical outcome of patients with chronic lymphocytic leukaemia (CLL). We defined the upper telomere length threshold at which telomere fusions occur and then used the mean of the telomere 'fusogenic' range as a prognostic tool. Patients with telomeres within the fusogenic range had a significantly shorter overall survival (P  <  0·0001; Hazard ratio [HR] = 13·2, 95% confidence interval [CI]  = 11·6-106·4) and this was preserved in early-stage disease patients (P  <  0·0001, HR=19·3, 95% CI = 17·8-802·5). Indeed, our assay allowed the accurate stratification of Binet stage A patients into those with indolent disease (91% survival at 10 years) and those with poor prognosis (13% survival at 10 years). Furthermore, patients with telomeres above the fusogenic mean showed superior prognosis regardless of their IGHV mutation status or cytogenetic risk group. In keeping with this finding, telomere dysfunction was the dominant variable in multivariate analysis. Taken together, this study provides compelling evidence for the use of high-resolution telomere length analysis coupled with a definition of telomere dysfunction in the prognostic assessment of CLL

A New Type of Plasma Wakefield Accelerator Driven by Magnetowaves

We present a new concept for a plasma wakefield accelerator driven by magnetowaves (MPWA). This concept was originally proposed as a viable mechanism for the "cosmic accelerator" that would accelerate cosmic particles to ultra high energies in the astrophysical setting. Unlike the more familiar Plasma Wakefield Accelerator (PWFA) and the Laser Wakefield Accelerator (LWFA) where the drivers, the charged-particle beam and the laser, are independently existing entities, MPWA invokes the high-frequency and high-speed whistler mode as the driver, which is a medium wave that cannot exist outside of the plasma. Aside from the difference in drivers, the underlying mechanism that excites the plasma wakefield via the ponderomotive potential is common. Our computer simulations show that under appropriate conditions, the plasma wakefield maintains very high coherence and can sustain high-gradient acceleration over many plasma wavelengths. We suggest that in addition to its celestial application, the MPWA concept can also be of terrestrial utility. A proof-of-principle experiment on MPWA would benefit both terrestrial and celestial accelerator concepts.Comment: revtex4, 4 pages, 6 figure

670 GHz Schottky Diode Based Subharmonic Mixer with CPW Circuits and 70 GHz IF

A coplanar waveguide (CPW) based subharmonic mixer working at 670 GHz using GaAs Schottky diodes. One example of the mixer has a LO input, an RF input and an IF output. Another possible mixer has a LO input, and IF input and an RF output. Each input or output is connected to a coplanar waveguide with a matching network. A pair of antiparallel diodes provides a signal at twice the LO frequency, which is then mixed with a second signal to provide signals having sum and difference frequencies. The output signal of interest is received after passing through a bandpass filter tuned to the frequency range of interest

A blind test of photometric redshift prediction

Results of a blind test of photometric redshift predictions against spectroscopic galaxy redshifts obtained in the Hubble Deep Field with the Keck Telescope are presented. The best photometric redshift schemes predict spectroscopic redshifts with a redshift accuracy of |Delta-z|<0.1 for more than 68 percent of sources and with |Delta-z|<0.3 for 100 percent, when single-feature spectroscopic redshifts are removed from consideration. This test shows that photometric redshift schemes work well at least when the photometric data are of high quality and when the sources are at moderate redshifts.Comment: 14 pp., accepted for publication in A