Reactions of dithianitronium hexafluoroarsenate(v) and some plasma studies

This work is chiefly concerned with the varied reactions of the compound dithianitronium hexafluoroarsenate(V), [SNS]AsF(_6).Chapter one provides a brief review of the properties and uses of [SNS][AsF(_6)], and chapter two outlines the experimental techniques required in this area of chemistry. Chapter three describes the synthesis and characterisation of ortho- substituted 1,3,2,4-dithiadiazohum salts, along with two crystal structures and reduction studies. The fourth and fifth chapters outline reactions of [SNS]AsF(_6)] with double and single bonds respectively, to form novel cations. Chapter six demonstrates the surface area expansion of silver when subjected to several plasma oxidation/reduction cycles. Appendix I outlines the synthesis and characterisation of the radical cation [NSSNCC(_6)H(_4)CNSNS]+.[AsF(_6)]. Appendix II illustrates the ability of [PhNSNSNPh][AsF(_6)] to polymerise thf. Appendix III lists colloquia, lectures and seminars attended by the author, and appendix IV contains supplementary crystallographic data

Is There Enhanced Depletion of Gas-Phase Nitrogen in Moderately Reddened Lines of Sight?

We report on the abundance of interstellar neutral nitrogen (NI) for 30 sightlines, using data from the Far Ultraviolet Spectroscopic Explorer (FUSE) and the Hubble Space Telescope (HST). NI column densities are derived by measuring the equivalent widths of several ultraviolet absorption lines and subsequently fitting those to a curve of growth. We find a mean interstellar N/H of 51+/-4 ppm. This is below the mean found by Meyer et al. of 62(+4,-3) ppm (adjusted for a difference in f-values). Our mean N/H is similar, however, to the (f-value adjusted) mean of 51+/-3 ppm found by Knauth et al. for a larger sample of sightlines with larger hydrogen column densities comparable to those in this study. We discuss the question of whether or not nitrogen shows increased gas-phase depletion in lines of sight with column densities log(H_tot) >~ 21, as claimed by Knauth et al. The nitrogen abundance in the line of sight toward HD 152236 is particularly interesting. We derive very small N/H and N/O ratios for this line of sight that may support a previous suggestion that members of the Sco OB1 association formed from an N-deficient region.Comment: Accepted in The Astrophysical Journal, 9/2006 (expected pub. date: 1/2007) 38 pages, 5 figures (4 color

Directed evolution strategies for improved enzymatic performance

The engineering of enzymes with altered activity, specificity and stability, using directed evolution techniques that mimic evolution on a laboratory timescale, is now well established. However, the general acceptance of these methods as a route to new biocatalysts for organic synthesis requires further improvement of the methods for both ease-of-use and also for obtaining more significant changes in enzyme properties than is currently possible. Recent advances in library design, and methods of random mutagenesis, combined with new screening and selection tools, continue to push forward the potential of directed evolution. For example, protein engineers are now beginning to apply the vast body of knowledge and understanding of protein structure and function, to the design of focussed directed evolution libraries, with striking results compared to the previously favoured random mutagenesis and recombination of entire genes. Significant progress in computational design techniques which mimic the experimental process of library screening is also now enabling searches of much greater regions of sequence-space for those catalytic reactions that are broadly understood and, therefore, possible to model. Biocatalysis for organic synthesis frequently makes use of whole-cells, in addition to isolated enzymes, either for a single reaction or for transformations via entire metabolic pathways. As many new whole-cell biocatalysts are being developed by metabolic engineering, the potential of directed evolution to improve these initial designs is also beginning to be realised

Ionic Liquid-Based Microchannels for Highly Sensitive and Fast Amperometric Detection of Toxic Gases

Ionic liquid (IL)-based microchannels sensors have been fabricated and employed for the detection of toxic ammonia (NH3) and hydrogen chloride (HCl) gases, with enhanced sensitivity and response times compared to conventional electrodes. Electrochemical techniques were employed to understand the behaviour of these highly toxic gases in two ionic liquids, [C4mpyrr][NTf2] and [C2mim][NTf2], on a gold modified microchannels electrode. The limits of detection (LODs) obtained in [C4mpyrr][NTf2] for NH3 (3.7 ppm) and in [C2mim][NTf2] for HCl (3.6 ppm) were lower than the current Occupational Safety and Health Administration Permissible Exposure Limit (OSHA PEL) for the two gases (25 ppm for NH3 and 5 ppm for HCl). The response time of the sensor is 15 s with a sensitivity of 143 nA ppm-1 and 14 nA ppm-1 for HCl and NH3, respectively. These results demonstrate the superiority of IL-based microchannels sensors for detecting toxic gases, when compared to commercially available sensors or traditional IL-based sensor designs, where high sensitivity or fast response time is still a challenge

Mixed configuration-interaction and many-body perturbation theory calculations of energies and oscillator strengths of J=1 odd states of neon

Ab-initio theory is developed for energies of J=1 particle-hole states of neutral neon and for oscillator strengths of transitions from such states to the J=0 ground state. Hole energies of low-Z neonlike ions are evaluated.Comment: 5 pages, 1 figure, 4 table

A machine learning‑based image segmentation method to quantify in vitro osteoclast culture endpoints

Quantification of in vitro osteoclast cultures (e.g. cell number) often relies on manual counting methods. These approaches are labour intensive, time consuming and result in substantial inter- and intra-user variability. This study aimed to develop and validate an automated workflow to robustly quantify in vitro osteoclast cultures. Using ilastik, a machine learning-based image analysis software, images of tartrate resistant acid phosphatase-stained mouse osteoclasts cultured on dentine discs were used to train the ilastik-based algorithm. Assessment of algorithm training showed that osteoclast numbers strongly correlated between manual- and automatically quantified values (r = 0.87). Osteoclasts were consistently faithfully segmented by the model when visually compared to the original reflective light images. The ability of this method to detect changes in osteoclast number in response to different treatments was validated using zoledronate, ticagrelor, and co-culture with MCF7 breast cancer cells. Manual and automated counting methods detected a 70% reduction (p < 0.05) in osteoclast number, when cultured with 10 nM zoledronate and a dose-dependent decrease with 1-10 μM ticagrelor (p < 0.05). Co-culture with MCF7 cells increased osteoclast number by ≥ 50% irrespective of quantification method. Overall, an automated image segmentation and analysis workflow, which consistently and sensitively identified in vitro osteoclasts, was developed. Advantages of this workflow are (1) significantly reduction in user variability of endpoint measurements (93%) and analysis time (80%); (2) detection of osteoclasts cultured on different substrates from different species; and (3) easy to use and freely available to use along with tutorial resources

Multiconfiguration electron density function for the ATSP2K-package

A new ATSP2K module is presented for evaluating the electron density function of any multiconfiguration Hartree-Fock or configuration interaction wave function in the non relativistic or relativistic Breit-Pauli approximation. It is first stressed that the density function is not a priori spherically symmetric in the general open shell case. Ways of building it as a spherical symmetric function are discussed, from which the radial electron density function emerges. This function is written in second quantized coupled tensorial form for exploring the atomic spherical symmetry. The calculation of its expectation value is performed using the angular momentum theory in orbital, spin, and quasispin spaces, adopting a generalized graphical technique. The natural orbitals are evaluated from the diagonalization of the density matrix

High Resolution HST-STIS Spectra of CI and CO in the Beta Pictoris Circumstellar Disk

High resolution FUV echelle spectra showing absorption features arising from CI and CO gas in the Beta Pictoris circumstellar (CS) disk were obtained on 1997 December 6 and 19 using the Space Telescope Imaging Spectrograph (STIS). An unsaturated spin-forbidden line of CI at 1613.376 A not previously seen in spectra of Beta Pictoris was detected, allowing for an improved determination of the column density of CI at zero velocity relative to the star (the stable component), N = (2-4) x 10^{16} cm^{-2}. Variable components with multiple velocities, which are the signatures of infalling bodies in the Beta Pictoris CS disk, are observed in the CI 1561 A and 1657 A multiplets. Also seen for the first time were two lines arising from the metastable singlet D level of carbon, at 1931 A and 1463 A The results of analysis of the CO A-X (0-0), (1-0), and (2-0) bands are presented, including the bands arising from {13}^CO, with much better precision than has previously been possible, due to the very high resolution provided by the STIS echelle gratings. Only stable CO gas is observed, with a column density N(CO) = (6.3 +/- 0.3) x 10^{14} cm{-2}. An unusual ratio of the column densities of {12}^CO to {13}^CO is found (R = 15 +/- 2). The large difference between the column densities of CI and CO indicates that photodissociation of CO is not the primary source of CI gas in the disk, contrary to previous suggestion.Comment: 13 pages, including 6 figures. LaTex2e (emulateapj5.sty). Accepted for publication in Ap